Single-package ambient-cured crosslinkable copolymers of vinyl branched ester and vinyl silane compositions and uses thereof

Abstract

This invention relates to a method for producing a stable copolymer composition, comprising adding an organic solvent, an alkyl-alkoxysilane and / or a C1-C9 alcohol, a monomer, and a free radical initiator to a reactor. The copolymer composition is based on a vinyl-branched ester polymer modified with a vinylsilane and a dehydrating agent. The copolymer composition can be formulated to a desired viscosity, can be applied using conventional techniques, and can be optimized for curing as a single-package system at room temperature in the presence of a suitable catalyst.

Description

Technical Field

[0001] This invention relates to a method for producing a stable resin for use in low-temperature (<80°C) moisture-curable single-package coatings. Specifically, silane copolymers are prepared by free radical polymerization in the presence of non-polymerizable dehydrating agents such as alkoxysilanes, orthoesters or titanates and / or C1-C9 alcohols.

[0002] The coating composition comprises:

[0003] A) Based on silane-vinyl ester copolymers,

[0004] B) Optional pigments and fillers,

[0005] C) Solvent,

[0006] D) Paint additives,

[0007] E) Dehydrating agents such as alkoxysilanes, vinylsilanes, orthoesters, titanates, preferably vinylsilanes, and most preferably vinyltrimethoxysilanes.

[0008] F) Optionally, C1-C6 alcohols,

[0009] G) optionally, a polysiloxane polymer, and

[0010] H) Adhesion accelerator,

[0011] I) Solidified catalyst.

[0012] The polymer composition is particularly suitable for environmentally curable (<60°C) coatings and adhesives applications. Background Technology

[0013] The use of silanes in single-package (1K) acrylic coating formulations is well-known, particularly since acrylic-silane coating compositions have a recognized curing rate and form a product film with good physicochemical properties upon curing. However, a significant drawback of these compositions is their short shelf life. For decades, industry has explored options to address this major shortcoming.

[0014] US4,043,953 relates to a coating composition that is moisture-curable at ambient temperature, wherein improved shelf life is achieved by the invention, the composition comprising an acrylic-silane interpolymer derived from a monomer that does not contain active hydrogen atoms, a curing accelerating catalyst, and the structural formula: X n Si(OR) 4-n Blends of monomeric hydrolyzable reactive organosilicon compounds.

[0015] EP0007765 comments on the aforementioned literature as follows: While the method disclosed in US 4,043,953 undoubtedly improves the stability of polymeric organosilanes, we have found certain limitations, particularly when the polymeric organosilane is intended to be used as a binder additive rather than as a coating itself. For various reasons, the viscosity stability requirements are somewhat more stringent when using the polymeric organosilane as a binder additive rather than as a coating. Therefore, EP0007765 and EP0050249 have discovered a synergistic effect of the presence of low molecular weight alcohols and monomerically hydrolyzable reactive compounds on the stability of acrylic-silane interpolymers.

[0016] Twenty years later, WO0198419 still sought to propose a so-called single-packaging system for the catalyst through physical isolation, typically packaged separately from the (pigment-containing) polymer. The components were then mixed together just before the paint was applied. The use of "double-layered" cans made a pseudo-single-packaging system, where the catalyst was stored separately from the paint in one can, allowing for rapid drying and stable storage.

[0017] WO04067576 confirms that stable coating formulations can be obtained when the acrylic polymer is substantially free of functional groups capable of reacting with polysiloxanes or catalysts. The coating properties are not disclosed in this document.

[0018] Therefore, there is a need for compositions with reduced curing cycles and temperatures, while minimizing the effects of undesirable chemicals, as well as methods for applying such compositions. Most preferably, the industry seeks systems that can cure at room temperature after application and remain stable in the can before application. Summary of the Invention

[0019] Embodiments of the present invention relate to a method for obtaining a polymer composition exhibiting improved stability and a method for applying the polymer composition.

[0020] In one aspect of the invention, a method for producing a polymer composition comprising an organosilane copolymer and a nonpolymerizable dehydrating agent (E), the organosilane copolymer being derived from at least A1 and A2 monomers, wherein the A1 monomer comprises a vinyl ester monomer and the A2 monomer comprises a vinylsilane monomer, the nonpolymerizable dehydrating agent being selected from: alkoxysilanes, orthoesters, titanates, zirconates, oxazolines, sulfates and / or C1-C9 alcohols and combinations thereof.

[0021] In another aspect of the invention, a method of applying a composition comprising an organosilane copolymer and a dehydrating agent, the organosilane copolymer being derived from at least A1 and A2 monomers, wherein the A1 monomer comprises a vinyl ester monomer and the A2 monomer comprises a vinylsilane monomer, the dehydrating agent being selected from: vinylsilanes, orthoesters, titanates, zirconates, oxazolines, sulfates, and / or C1-C9 alcohols and combinations thereof. The composition may further comprise one or more materials selected from: solvents, catalysts, pigments, fillers, paint additives, C1-C6 alcohols, polysiloxane polymers, adhesion promoters, and combinations thereof. The composition may further be cured in the presence of moisture. Detailed Implementation

[0022] This invention provides a method for obtaining a polymer composition exhibiting improved stability and a method for applying the polymer composition. The method comprises reacting a vinyl ester monomer, a silane-functionalized monomer, and an organic peroxide at a reaction temperature of 80°C-200°C in the presence of a non-polymerizable desiccant selected from alkoxysilanes, orthoesters, or titanates, preferably alkyl-alkoxysilanes, and / or C1-C9 alcohols. Preferred alkyl-alkoxysilanes are methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, or blends thereof, and / or C1-C9 alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, isononol, and combinations thereof. The combination of alkyl-alkoxysilanes and alcohols has been found to have a synergistic effect on the stability of the formulation. The alkyl-alkoxysilanes and C1-C9 alcohols are present in a weight ratio of 100 / 0 to 30 / 70. The desiccant is present in a weight ratio of 1 / 100 to 15 / 85 based on the total amount of monomers used. The polymer composition must contain an organosilane copolymer and a desiccant. The desiccant may be selected from vinylsilanes, alkylsilanes, orthoesters, titanates, zirconates, oxazolines, sulfates, and / or C1-C9 alcohols and combinations thereof. The polymer composition can be used in coatings and other applications. The composition may further contain one or more materials selected from: solvents, catalysts, pigments, fillers, paint additives, C1-C6 alcohols, polysiloxane polymers, adhesion promoters, and combinations thereof.

[0023] The polymer composition can be formulated to a desired viscosity for application using conventional coating techniques, and the curing rate can be optimized in the presence of a suitable catalyst. The polymer composition may contain an organosilane copolymer and a dehydrating agent. The organosilane copolymer may comprise 5 wt% to 80 wt%, for example 10 wt% to 60 wt%, or for example 20 wt% to 50 wt% of the polymer composition. The dehydrating agent may comprise 0.05 wt% to 10 wt%, for example 0.1 wt% to 5 wt%, or for example 1 wt% to 3 wt% of the polymer composition.

[0024] The polymer composition comprises an organosilane copolymer. In one embodiment, the organosilane copolymer is derived from at least A1 and A2 monomers, wherein the A1 monomer comprises a vinyl ester monomer and the A2 monomer comprises a silane-functionalized monomer such as vinylsilanetrimethoxy, vinyltriethoxysilane, methylvinyldiethoxysilane, acryloylsilane monomer, methacrylsilane monomer, or combinations thereof. The copolymer may also be derived from one or more optional monomers selected from: monomers comprising vinyl acetate (A3 monomers), monomers comprising acrylates, methacrylates (A4 monomers), or combinations thereof, monomers comprising any other vinyl monomers not comprising vinyl esters or vinyl silanes (A5 monomers), and combinations thereof.

[0025] A1 monomers containing vinyl ester monomers can have the following formula:

[0026]

[0027] R1, R2, and R3 are hydrogen atoms or alkyl groups having 1-15 carbon atoms, and the total number of carbon atoms in R1, R2, and R3 is 1-20. In one embodiment, the total number of carbon atoms in R1, R2, and R3 is 5-12. Suitable vinyl esters include those derived from branched acids, such as trimethylacetic acid, 2-ethylhexanoic acid, and neo-acids (also known as versatic acid). TM The vinyl ester monomers are derived from Hexion Inc., and the total number of carbon atoms in R1, R2, and R3 is 7, 8, 9, and 10. Examples of these vinyl ester monomers include trimethylvinyl acetate, vinyl 2-ethylhexanoate, vinyl neodecanoate, and vinyl neononanoate, and combinations thereof. Commercially available examples of vinyl ester monomers include VeoVa 9, VeoVa 10, and combinations thereof, which are commercially available from Hexion Inc., Columbus, Ohio.

[0028] The vinyl ester monomer (A1 monomer) can account for 15 wt% to 95 wt% of the total weight percentage (100 wt%) of the monomer, for example, 30 wt% to 95 wt%, 50 wt% to 90 wt%.

[0029] Vinylsilane monomers (A2 monomers) may include the following formula:

[0030]

[0031] R4, R5, and R6 are alkyl groups having 1-4 carbon atoms. Suitable vinylsilanes and R4-R6 are methoxy or ethoxy. Suitable examples of these vinylsilane monomers include vinylsilanetrimethoxy, vinyltriethoxysilane, methylvinyldiethoxysilane, and combinations thereof. Commercial examples of vinylsilane monomers include Silquest A171 and Silquest A151, and combinations thereof, commercially available from MomentivePerformance Materials Inc., New York, USA (for the United States, country, or city and state).

[0032] Monomer A2 containing acryloylsilane or methacrylsilane can also be used in copolymers. Suitable examples of acryloylsilane monomers include methacryloxypropylmethyldimethoxysilane, methacryloxytrimethoxysilane, and methacryloxytriethoxysilane, and combinations thereof. Commercial examples of acryloylsilane monomers include Silquest A174, Silquest*Y-11878, and combinations thereof, commercially available from Momentive Performance Materials Inc., New York, USA (for the United States, country, or city and state).

[0033] Vinylsilane monomers (A2 monomers) can comprise 1 wt% to 35 wt% of the total monomer weight percentage (100 wt%), for example 2 wt% to 25 wt%, or 2 wt% to 20 wt%. Monomers containing acryloylsilanes (A2 monomers) can comprise 0 wt% to 25 wt% of the total monomer weight percentage (100 wt%), for example 0 wt% to 15 wt%, or 5 wt% to 10 wt%.

[0034] Monomers containing vinyl acetate (A3 monomers) can account for 0 wt% to 75 wt% of the total weight percentage (100 wt%) of the monomers, for example, 0 wt% to 60 wt%, 20 wt% to 50 wt%.

[0035] Monomers comprising acrylates, methacrylates, or combinations thereof (A4 monomers) can also be used in copolymers. Suitable examples of A4 monomers include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isopropyl methacrylate, isobornyl methacrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, and combinations thereof. Monomers comprising acrylates, methacrylates, or combinations thereof (A4 monomers) can account for 0 wt% to 97 wt% of the total weight percentage (100 wt%) of the monomers, for example, 0 wt% to 40 wt%, 5 wt% to 25 wt%.

[0036] Any other vinyl monomer (A5 monomer) containing non-vinyl esters or vinyl silanes can also be used in copolymers. Suitable examples of A5 monomers include N-vinylpyrrolidone, vinyl ethers, acrylic acid, methacrylic acid, and combinations thereof.

[0037] Any other vinyl monomer (A5 monomer) containing non-vinyl esters or vinyl silanes may be 0 wt% to 30 wt% of the total weight percentage (100 wt%) of the monomer, for example 0 wt% to 10 wt%, 0 wt% to 5 wt%.

[0038] In one embodiment of the invention, the copolymer derived from at least A1 and A2 monomers comprises:

[0039] 10wt%-95wt% of A1 monomer;

[0040] 5wt%-35wt% of A2 monomer;

[0041] 0 wt% - 75 wt% of A3 monomers;

[0042] 0wt%-97wt% A4 monomers; and

[0043] 0wt%-30wt% of A5 monomers;

[0044] Wherein wt% is based on the total weight of at least A1 and A2 monomers, and the total weight percentage is 100wt%.

[0045] The number average molecular weight of the copolymer can be 1,000 Daltons to 40,000 Daltons, for example 2,000 Daltons to 25,000 Daltons, 3,500 Daltons to 12,000 Daltons.

[0046] Suitable dehydrating agents for use in paint compositions may be selected from vinylsilanes, orthoesters, titanates, zirconates, oxazolines, calcium sulfate, calcium oxide, isocyanate zeolite-based molecular sieves, and combinations thereof. Examples of dehydrating agents include vinyltrimethoxysilane, vinyltriethoxysilane, trimethyl orthoformate, triethyl orthoformate, triethyl orthoacetate, tetrabutyl titanate, chelates of diisobutoxytitanium and ethyl acetoacetate, and combinations thereof.

[0047] In one embodiment, the polymer composition comprises a coating formulation containing copolymers based on the monomers described herein, dehydrating agents described herein, catalysts, organic solvents, and optionally one or more additives.

[0048] In one embodiment, the copolymer may comprise 10 wt% to 90 wt% of the total weight percentage (100 wt%) of the coating formulation, for example 5 wt% to 80 wt% or 10 wt% to 60 wt%.

[0049] In one embodiment, the dehydrating agent may account for 0.05wt%-15wt% of the total weight percentage (100wt%) of the coating formulation, for example 0.1wt%-10wt%, 0.2wt%-5wt%.

[0050] Catalysts can be selected from strong acids, Lewis acids, carboxylic acids, bases such as amines, caustic bases, or alcohols, and combinations thereof. An alternative catalyst is a nitrate of a polyvalent metal ion, such as calcium nitrate, magnesium nitrate, aluminum nitrate, zinc nitrate, or strontium nitrate. Nitrates can also be covalently bonded to amines. Other catalysts include carbonates such as sodium carbonate or calcium carbonate. Commercial examples of catalysts include SiliXan Cat 240 (SiliXan GmbH), Nacurre 4054, Nacurre 5076, TYZOR TNBT, TYZOR9000, K-Kat 670 (King Industries), DBTDL (dibutyltin dilaurate) (Sigma Aldrich), 3-aminopropyltrimethoxysilane (Sigma), 2-ethylhexanoic acid, Versatic acid (Hexion), and combinations thereof. DBTDL is a preferred commercial catalyst for single-package systems used in coating formulations.

[0051] In one embodiment, the catalyst may comprise 0.1 wt% to 3 wt% of the total weight percentage (100 wt%) of the polymer composition, for example 0.2 wt% to 2 wt%, 0.3 wt% to 1 wt%.

[0052] Organic solvents can be selected from esters, ethers, ketones, aromatic compounds, and aliphatic compounds, and combinations thereof. Examples of organic solvents include butyl acetate, xylene, methylpentyl ketone, ethyl ethoxypropionate, and combinations thereof.

[0053] In one embodiment, the organic solvent may comprise 5 wt% to 60 wt% of the total weight percentage (100 wt%) of the polymer composition, for example 10 wt% to 55 wt% or 25 wt% to 50 wt%.

[0054] Optional additives may include one or more materials, including pigments, fillers, paint additives, C1-C6 alcohols, polysiloxane polymers [[xO-Si(R,R')ny]], adhesion promoters, and combinations thereof.

[0055] C1-C6 alcohols may be selected from methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and combinations thereof. The formulation may optionally contain 0 wt% of a C1-C6 alcohol. When present, the C1-C6 alcohol may constitute 0.1 wt% to 15 wt%, for example 1 wt% to 10 wt%, 2 wt% to 6 wt%, of the total weight percentage (100 wt%) of the polymer composition.

[0056] Suitable polysiloxane polymers can be selected from linear and branched polyalkylsiloxanes and combinations thereof. The formulation may contain 0 wt% of the polysiloxane polymer. When present, the polysiloxane polymer may constitute 1 wt% to 60 wt%, for example 5 wt% to 30 wt%, or 10 wt% to 25 wt%, of the total weight percentage (100 wt%) of the polymer composition.

[0057] Bonding accelerators may include epoxy silanes, alkoxy silanes and amino silanes, titanates and zirconates, and combinations thereof. Examples of suitable bonding accelerators may be selected from epoxypropyltrimethoxysilane, epoxy silane oligomers, and combinations thereof. Commercial examples of bonding accelerators include Silquest A-187, Silquest A-1871, and CoatOsil MP 200, commercially available from Momentive Performance Material, New York, USA.

[0058] The formulation may contain 0 wt% of a bonding accelerator. When present, the bonding accelerator may be 0.05 wt% to 4 wt% of the total weight percentage (100 wt%) of the polymer composition, for example 0.1 wt% to 3 wt%, 0.5 wt% to 2 wt%.

[0059] Pigments may include anatase and rutile types of titanium dioxide, lead oxide, zinc oxide, iron oxides, carbon black, and organic pigments and combinations thereof. Suitable examples of pigments may be selected from titanium dioxide, iron oxide, and combinations thereof. Formulations may contain 0 wt% pigment. When present, pigments may be 3 wt%-60 wt%, for example 5 wt%-50 wt%, or 5 wt%-40 wt%, of the total weight percentage (100 wt%) of the polymer composition. Preferred pigments are those with low water content (<2%). Titanium dioxide can be particularly subjected to hydrophobic surface treatments. Preferred grades of titanium dioxide have hydrophobic surface treatments, such as silicone. These include Ti-Pure from Chemours. TM R-350 and 2222 from Kronos GmbH.

[0060] Fillers may include barium sulfate and calcium sulfate, silicon oxides, silicates, and combinations thereof. The formulation may have 0 wt% filler. When present, fillers may be 5 wt% to 50 wt% of the total weight percentage (100 wt%) of the polymer composition, for example, 10 wt% to 40 wt%, or 10 wt% to 30 wt%.

[0061] Paint additives may include UV stabilizers, corrosion inhibitors, heat stabilizers, slip and scratch additives, biocides, thickeners, and combinations thereof. Formulations may contain 0 wt% paint additives. When present, paint additives may be 0.01 wt% to 8 wt%, for example 0.02 wt% to 6 wt%, or 0.02 wt% to 5 wt%, of the total weight percentage (100 wt%) of the polymer composition.

[0062] In one implementation, the formulation comprises:

[0063] 5wt%-80wt% organosilane copolymers;

[0064] 0.1wt%-10wt% dehydrating agent;

[0065] 5wt%-60wt% of solvent;

[0066] 0.05wt%-3.0wt% of catalyst;

[0067] 0wt%-15wt% C1-C6 alcohols;

[0068] 0wt%-60wt% polysiloxane polymers;

[0069] Approximately 0 wt% to approximately 4 wt% of adhesion promoters; and

[0070] 0wt%-60wt% of paint additives / pigments / fillers,

[0071] Wherein wt% is based on the total weight of the composition, and the total weight percentage is 100wt%.

[0072] The total weight percentage of the components in the polymer composition constitutes 100% by weight.

[0073] The present invention also relates to a single-package system having an extended shelf life of at least one month, the single-package system comprising a copolymer based on the monomers described herein, a dehydrating agent described herein, a catalyst, an organic solvent, and optionally one or more additives. The single-package system has the wt% components described herein for use in formulations.

[0074] To provide a better understanding of the invention (including its representative advantages), the following embodiments are provided.

[0075] Example

[0076] To enable those skilled in the art to more fully understand the invention presented herein, the following procedures and embodiments are described. Unless otherwise indicated, the following units of measurement and definitions apply to this application: total parts and percentages are by weight; temperature is in degrees Celsius (°C).

[0077] experiment

[0078] In the following embodiments, data is exported according to the following procedure.

[0079] Solid content: Solid content is the weight percentage of non-volatile materials present in a coating formulation. It is measured by the weight loss after 1 hour in a ventilated oven at 110°C.

[0080] Viscosity: Viscosity is a measure of the flow resistance of a polymer formulation. Viscosity is measured using a Brookfield viscometer.

[0081] Molecular weight: Molecular weight is given as weight-average and number-average Mw, and it is determined by gel permeation chromatography using polystyrene as a reference, tetrahydrofuran as the eluent and refractive index as the detector, as described in DIN standard 55672.

[0082] Storage lifespan: Shelf life is an assessment of the period during which a polymer composition can be used for a specific application. It is typically determined by the time it takes for the formulated system to reach twice its initial viscosity in a sealed container once applied.

[0083] Shelf life: Shelf life is an assessment of the time a formulated adhesive can be stored under typical storage conditions without losing its properties. Shelf life is typically determined by measuring changes in viscosity.

[0084] stability: The stability of the 1K moisture-curable system is considered by examining the maximum amount of water % that can be added to the adhesive before gelation in a sealed autoclave.

[0085] The following embodiments are provided to illustrate the invention and should not be construed as limiting the scope of the invention.

[0086] Examples 1-8:In a glass reactor equipped with a stirrer and nitrogen inflow, the initial reactor charge was poured into the reactor, and a nitrogen layer (10 ln / h) was applied. The stirrer was set to 80 RPM. The temperature was set to 115 °C. A monomer mixture was prepared by mixing the monomer and the initiator. Once the reactor temperature was reached, an initiator was added, and the nitrogen inflow was stopped. The monomer mixture was then added to the reactor over a period of 4 hours. At the end of the addition, an accelerator containing the initiator and solvent was added over 1 hour at 115 °C. The reactor was then maintained at the same temperature for another hour. Finally, the reactor was cooled to below 80 °C, and the product was discharged.

[0087]

[0088] The best stability results (lowest PDI, highest maximum water content before gelation) were obtained using butanol in the initial reactor charge (Example 4), MTMS (Example 5), or a combination of butanol and MTMS (Example 8).

[0089] Improved stability: Added later (refer to the formula - acrylate-free).

[0090] Examples 8-18:

[0091] Example 1 was mixed with different stabilizers, and stability was evaluated by adding ppm of water to the system until gelation.

[0092]

[0093] The best stability results (the highest maximum water content before gelation) were obtained using vinyltrimethoxysilane (Example 12) as a dehydrating agent or by a combination of alcohol and vinyltrimethoxysilane (Example 18).

[0094] Improved stability: Synthesis (using high-Tg acrylates instead of VV9)

[0095] Examples 19-26:In a glass reactor equipped with a stirrer and a nitrogen flow, the initial reactor charge was poured into the reactor, and a nitrogen layer (10 ln / h) was applied. The stirrer was set to 80 RPM. The temperature was set at 115°C for Examples 19-20 and 105°C for Examples 21-26. A monomer mixture was prepared by mixing the monomer and the initiator. Once the reactor temperature was reached, an initiator was added, and the nitrogen flow was stopped. The monomer mixture was then added to the reactor over a period of 4 hours. At the end of the addition, an accelerator comprising the initiator and solvent was added over 1 hour at 115°C for Examples 19-20 and 105°C for Examples 21-26. The reactor was then maintained at the same temperature for another hour. The reactor was finally cooled to below 80°C, and the product was discharged.

[0096] When high-Tg acrylates were used instead of VeoVa 9, Examples 22-24 exhibited stable methods and stable products upon discharge. Example 25 gelled during the process and was successfully stabilized in Example 26 by increasing the alcohol level in the initial reactor charge.

[0097] Procedures for coating formulations: First, the resin was diluted to a viscosity of 100-200 cPs using a (synthetic) solvent. Then, the catalyst DBTDA was added to the diluted resin at an activity level of 0.5%. Subsequently, the prepared resin was applied to the panel in a 100 μm wet thickness using a Mayer rod and allowed to dry at 23 ± 2 °C and 50 ± 5% relative humidity.

[0098]

[0099]

[0100] The performance at application showed that materials based on VeoVa 9 and those based on high Tg acrylates had similar drying processes.

[0101] High-gloss formulation: synthesized in the presence of styrene.

[0102]

[0103] The optimal synthesis results at discharge were obtained by combining a portion of styrene with VeoVa 10 in the initial reactor charge (Examples 38-39).

[0104] Examples 36-39 were applied by first diluting the system to a viscosity of 100-200 cPs with a synthetic solvent. Then, the catalyst DBTDA was added to the diluted resin at a level of 0.5% active material. Subsequently, the prepared resin was applied to a panel with a wet thickness of 100 μm using a Mayer rod and allowed to dry at 23 ± 2 °C and 50 ± 5% relative humidity.

[0105]

[0106] The optimal gloss was obtained using Example 38, which contained the highest styrene content.

[0107] Additional embodiments with VAM (including better conversion rates)

[0108] Examples 46 and 48 were compared by GPC prior to the accelerator step. Example 46 exhibited approximately 11% area of ​​unconverted monomer prior to the accelerator step, while Example 48 exhibited 4%. Complete conversion was achieved in Example 48 when an additional 1 hour was used without the addition of an accelerator.

[0109] Samples 51, 52 and 53 were prepared as Examples 36-39.

[0110]

[0111]

[0112] Example 54: In a glass reactor equipped with a stirrer and nitrogen inflow, the initial reactor charge was poured into the reactor, and a nitrogen layer (10 ln / h) was applied. The stirrer was set to 80 RPM. The temperature was set to 115 °C. A monomer mixture was prepared by mixing the monomer and the initiator. Once the reactor temperature was reached, an initiator was added, and the nitrogen inflow was stopped. The monomer mixture was then added to the reactor over a period of 4 hours. At the end of the addition, an accelerator containing the initiator and solvent was added over 1 hour at 115 °C. The reactor was then maintained at the same temperature for another hour. Finally, the reactor was cooled to below 80 °C, and the product was discharged.

[0113]

[0114]

[0115] Procedures for coating formulations: First, the resin was diluted to a viscosity of 300 cPs using a solvent (butyl acetate). Then, the catalyst DBTDA was added to the diluted resin at an activity level of 1%. For Examples 55 and 56, the additive addition level was 3% of the active material. Subsequently, the formulated resin was applied to a stainless steel panel with a Mayer rod to a wet thickness of 150 μm and allowed to dry at 23 ± 2 °C and 50 ± 5% relative humidity.

[0116] Adhesion on stainless steel:

[0117] After 7 days of drying, the adhesiveness was graded according to the tape test in accordance with ASTM D 3359.

[0118]

[0119] When additives are added to the resin, optimal adhesion results are obtained on stainless steel panels.

[0120] Adhesion on epoxy primer test:

[0121] A fast-drying, high-solids epoxy primer (which is recommended as a durable protective barrier in coating systems for harsh corrosive environments) was applied to a stainless steel panel with a Mayer rod at a wet thickness of 150 μm and left to dry for 21 days at 23±2°C and 50±5% relative humidity.

[0122] The resin was diluted to a viscosity of 300 cPs using a solvent (butyl acetate). Then, the catalyst DBTDL was added to the diluted resin at an activity level of 1%. For Example 2, the additive addition level was 3% active material. Subsequently, the formulated resin was applied to an epoxy primer with a wet thickness of 150 μm using a Mayer rod and allowed to dry for 7 days at 23 ± 2 °C and 50 ± 5% relative humidity.

[0123]

[0124] Improved adhesion to epoxy primers was observed by adding 3% of the active ingredient γ-aminopropyltrimethoxysilane to the resin.

[0125] Paint adhesion in epoxy primer test:

[0126] Pigment-coated exterior coatings were prepared using the resin from Example 54:

[0127]

[0128] Add items 1-5 to a suitably sized stainless steel mixing container. Begin low-speed mixing with Cowles-type dispersing blades to homogenize the materials. With moderate mixing, slowly begin adding item 6. As viscosity builds, increase the disperser speed. Add all pigment to the container, increasing the speed until a toroidal flow or doughnut effect is achieved. After a few minutes, stop mixing and scrape the container walls with a spatula, then restart the dispersion process. After 20 minutes, stop the mixer and check the fineness with a Hegman ruler. It should be above 7. If not, continue grinding for another 20 minutes. Once the fineness is achieved, add the remaining ingredients (items 7 and 8). Then gradually add the solvent (items 9 and 10), reducing the mixing speed if necessary to avoid phase loss. Filter through a 375 μm mesh into a metal can container. If a viscosity of 70 KU is required, add additional solvent.

[0129] The catalyst DBTDL was added to the diluted paint at an activity level of 1% based on polymer solids. For Examples 55-61, the addition levels of the additive are as described in the table. Subsequently, the prepared paint was applied to the epoxy primer with a wet thickness of 150 μm using a Mayer rod and allowed to dry for 7 days at 23 ± 2 °C and 50 ± 5% relative humidity.

[0130]

[0131] It has been observed that improved adhesion to epoxy primers is achieved by adding one of the listed additives.

[0132] Improved paint gloss and stability: using a new dispersant

[0133] Grinding base material 62 63 1Veova silane Resins 54 499.2 499.2 2a Dispersant Disperplast P 13.4 2b dispersant Disperbyk 110 4.7 3 Additives BYK 358N 4.8 4.8 4 Additives BYK 077 4.8 4.8 5 Additives Solthix 250 9.7 9.7 6 Titanium dioxide Ti-Pure TS 6200 271 271 Paint mixing 7 Additives Tinuvin 123 11.5 11.5 8 Additives Tinuvin 1130 14.8 14.8 9 Solvents Ethyl ethoxypropionate 122.0 122.0 10 solvents Methylpentyl ketone 57.4 57.4 Solid content % 69.4 69.9

[0134] The paint was prepared according to the procedure described above. The catalyst DBTDL was added to the diluted paint at an activity level of 1%. Subsequently, the prepared paint was applied to a stainless steel panel with a wet thickness of 150 μm using a Mayer rod and allowed to dry for 7 days at 23±2°C and 50±5% relative humidity.

[0135] Example 63, which contains Disperplast P as a dispersant, achieved the best gloss of the lacquer.

[0136] The graffiti resistance of the paint in Example 63 was evaluated using a manual solvent wiping method in accordance with ASTM D6578.

[0137] The marking materials used:

[0138] 1. Solvent-based ink marker, blue

[0139] 2. Solvent-based spray paint, red

[0140] 3. Crayon, black

[0141] The cleaning materials evaluated:

[0142] 1. Dry, 100% acrylic white substrate

[0143] 2. Citrus-based cleaner

[0144] 3. Isopropanol

[0145] 4. Methyl ethyl ketone

[0146] The solvent-based ink marker (blue) was applied to the paint of Example 63 and removed after 25 cycles with cleaning material 1, 25 cycles with cleaning material 1, and 3 cycles with cleaning material 3.

[0147] The solvent-based paint (red) was removed after 25 cycles of cleaning materials 1, 2, and 3, and after 2 cycles of cleaning material 4.

[0148] Remove the black crayon by cleaning material 1 after 12 cycles.

Claims

1. A method for producing a stable copolymer composition, the method comprising the following steps: Monomer mixture A is subjected to free radical copolymerization in the following conditions. 0.5-10 wt% of a non-polymerizable desiccant, wherein the non-polymerizable desiccant is an alkoxysilane, an orthoester, or a combination thereof. 0.5-15 wt% of C1-C9 alcohols, and 0-40wt% of other solvents or additives; The monomer mixture A contains, by weight percentage of the total monomers in the monomer mixture A: -A1: 10-95 wt% of the following vinyl ester monomers: R1, R2, and R3 are hydrogen or alkyl groups with 1-15 carbon atoms, and the total number of carbon atoms in R1, R2, and R3 is 7-10 carbon atoms. -A2: 3-35 wt% of the following silane functionalized monomers: or R4, R5, and R6 are alkyl or alkoxy groups having 1-4 carbon atoms. -A3: 60-0 wt% vinyl acetate, -A4: 25-0 wt% acrylate or methacrylate monomers, and -A5: 0-30wt% of other copolyvinyl monomers.

2. The method according to claim 1, wherein the alkoxysilane is methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane or ethyltriethoxysilane, and the orthoester is orthoformate orthoacetate.

3. The method according to any one of claims 1-2, wherein the C1-C9 alcohol is propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, isononol, or a combination thereof.

4. The method according to claim 3, wherein the C1-C9 alcohol is butanol.

5. The method according to any one of claims 1-2, wherein the monomer mixture A comprises: 15wt%-95wt% of A1 monomer; and 5wt%-35wt% of A2 monomer.

6. The method according to any one of claims 1-2, wherein the monomer mixture A comprises: 10wt%-95wt% of A1 monomer; 5wt%-35wt% of A2 monomer; A3 monomers ranging from 0 wt% to 60 wt%; 0wt%-25wt% A4 monomer; 0wt%-30wt% of A5 monomers.

7. A stable copolymer composition prepared by the method according to any one of claims 1-6.

8. A formulation comprising the stable copolymer composition according to claim 7 and one or more materials selected from the group consisting of solvents, catalysts, pigments, fillers, paint additives, C1-C6 alcohols, polysiloxane polymers, adhesion promoters, and combinations thereof.

9. The formulation according to claim 8, wherein the formulation comprises: The stable copolymer composition comprises 5wt%-80wt% of this copolymer. 0.1wt%-10wt% of dehydrating agent; Solvents of 5wt%-60wt%; Catalysts ranging from 0.05 wt% to 3.0 wt%; 0wt%-15wt% C1-C6 alcohols; 0wt%-60wt% polysiloxane polymers; 0wt%-4wt% of adhesion accelerator; and 0wt%-60wt% of paint additives, pigments, fillers, or combinations thereof, The total weight percentage is 100 wt%.

10. The formulation according to claim 8 or 9, wherein the formulation is a single-package ambient temperature curing paint formulation.

11. An article coated with the formulation according to any one of claims 8-10.

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