Patent Publication Number: US-2023144691-A1

Title: Manganese-bearing polymer complexes

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a continuation of U.S. patent application Ser. No. 17/618,940 filed on Dec. 14, 2021, which is a U.S. National Stage application of International Patent Application No. PCT/EP2020/061309, filed on Apr. 23, 2020, which claims the benefit of European Patent Application No. 19181433.4, filed on Jun. 20, 2019. 
    
    
     The present disclosure relates to manganese-bearing polymer complexes for use as driers in auto-oxidizable coating compositions, such as alkyd-based paints and varnishes, or as accelerators in unsaturated polyester resins (UPR). 
     Oil-modified polyester resins, referred to as alkyd resins, outline one of the major classes of surface coating resins. Since the early nineties, they have been widely applied in paints and varnishes, encompassing all the different protective surface coating market segments. Their popularity is no surprise as alkyd-based coatings are tough, strong adherent to many different types of surfaces, they are durable, impervious, and weather resistant and display excellent gloss appearance. Moreover, alkyds are largely derivable from agricultural products making them relatively green and biodegradable. In the last decade, much effort has also gone into alkyd-based coating compositions with low content of volatile organic compounds (VOC) and high content of sustainable bio-sourced ingredients. 
     Cobalt-based driers and accelerators, while still being considered as the most widely applicable primary driers and UPR accelerators on the market, are under regulatory pressure due to their potential toxicity. Manganese-based compounds such as carboxylates have therefore received significant attention as substitutes for cobalt-based compounds. Though widely used in ink drying applications at elevated temperature, manganese carboxylates are insufficiently reactive to oxidatively cure coatings like paints and varnishes in ambient conditions. Other problems are related to the yellowing induced by manganese-based driers, especially when used at higher concentrations. 
     It is known that the addition of specific chelating ligands can enhance the activity of manganese-based drying agents. Manganese driers containing Mn-bipyridyl and Mn-acetylacetonate are described by Gorkum et al. (EP1382648 A1). Although these driers reveal improved drying performance in comparison to traditional manganese carboxylates, the performance in terms of tack-free time and yellowing does not match that of cobalt-based driers. 
     In 2005, bridged di-nuclear manganese complexes [Mn IV (μ-O) 3 L 2 ](PF 6 ) 2 , in which the ligand L is 1,4,7-trimethyl-1,4,7-triazacyclononane, are described by Oyman et al. (Surf. Coatings. Int. Part B, Coatings Transactions, 88, 269, 2005). These complexes show a relatively good drying activity in different alkyd paint formulations. WO2011/098583, WO2011/098584 and WO2011/098587 also describe similar bridged di-nuclear manganese complexes. Replacing the (PF 6     −   ) 2  anion by a carboxylate anion in the bridged Mn-complex described by Oyman, results in improved drying activity. 
     Nevertheless, as described in WO2013092441, WO2013092442 and WO2014095670, these bridged di-nuclear manganese complexes are still inferior to traditional cobalt driers. The amount of manganese required to get acceptable paint drying can be significantly reduced by using a molar excess of 1,4,7-trimethyl-1,4,7-triazacyclononane. The drying rate can be improved while keeping yellowing of the paint under control. But despite all progress that has been made in the development of manganese driers, they still do not reach the performance of cobalt in many paint formulations. 
     An additional disadvantage of these manganese complexes is their relatively high water solubility, which implies also high bio-availability. To date, manganese carboxylates don&#39;t have any carcinogenic, mutagenic or toxic to reproduction (CMR) classification. However, manganese is a neurotoxic agent and its reproductive toxicity (“reprotoxicity”) and carcinogenicity are still questionable. Although manganese presents not as much of a health hazard as cobalt, a product with low water solubility—and thus lower bio-availability—of manganese is certainly preferred. 
     Low solubility manganese-based polymer driers are known from WO2012000934 and WO2014137307. They however offer inferior reactivity, which is still adequate for inks but too low for use in coating formulations at ambient conditions. One reason for that might be a steric hinderance effect. For example, Egboh teaches in his thesis “Synthesis and characterization of polyurethane ionomers and graft copolymers” (University of London, 1982, page 62) that a sterically hindered polymer molecule is relatively inactive for physical reasons, for the active groups cannot be reached by the reagents due to the size, number and close proximity of other substituents on the molecule. These substituent groups inhibit the approach of reagents and tend to diminish the reactivity of the functional groups. As manganese is part of the polymer backbone, also the formation of bridged di-nuclear manganese complexes, as described in the above citations, is highly unlikely. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein: 
         FIG.  1    is a chemical structure showing a manganese-bearing polymer having a repeating unit. 
         FIG.  2    is a series of chemical structures (L1-L13) showing potential chelating ligands. 
         FIG.  3    shows two chemical structures representing an ester or a polyester. 
         FIG.  4    is a shows two chemical structures representing a urethane or polyurethane. 
         FIG.  5    is a chemical structure representing an amide or polyamide. 
     
    
    
     Surprisingly, it has now been found that nitrogen-containing chelating ligands readily coordinate with manganese in the polymer chain, and that such manganese-based polymers do benefit greatly from an activating effect of these chelating ligands. The drying performance is drastically enhanced despite the steric hinderance effect. An additional unexpected finding is that the manganese-based polymer structure is apparently preserved after complexation, as corroborated by the fact that manganese remains essentially insoluble. This is beneficial with regards to the afore mentioned issues of reprotoxicity and carcinogenicity. 
     One other aspect, which is often overlooked, is the so-called “loss-of-dry” (LOD), i.e. the loss of drying performance as a function of paint storage time. This is of particular importance for pigmented systems in which the paint drier either adsorbs to the surface of pigments or is deactivated. Known compounds such as Mn-bipyridyl, Mn-acetylacetonate, and bridged di-nuclear manganese complexes can display significant loss-of-dry, even in presence of secondary driers. 
     Surprisingly, it has now been found that the chelated manganese polymers according to this invention offer strongly enhanced loss-of-dry performance compared to other known manganese-based complexes. This is particularly important as loss-of-dry otherwise severely limits the shelf life of the coating formulations. 
     A further advantage of the manganese-bearing polymer complexes is the enhanced compatibility and stability in alkyd-based paints. The properties of the manganese-based polymer driers can indeed easily be fine-tuned by altering the chemistry of the polymer backbone. 
     Moreover, yellowing remains very low. 
     The invention concerns a composition for use as drier in auto-oxidizable coatings or as accelerator in unsaturated polyester resins, comprising a manganese-bearing polymer having a repeating unit according to  FIG.  1   , wherein X is one or more groups from the list comprising a hydrocarbon chain, an ester, a polyester, a urethane, a polyurethane, an amide, and a polyamide; wherein n is 2; and at least one donor ligand from the list comprising bidentate, tridentate, pentadentate, and hexadentate nitrogen ligands comprising at least two chelating nitrogen atoms.  FIG.  1    shows that the manganese is part of the backbone of the polymer, wherein it is bound as a dicarboxylate. 
     It is to be noted that a composition “for use as drier in auto-oxidizable coatings”, has implicitly to be at least partially soluble in the targeted paints or varnishes, which are typically based on organic compounds, in particular on oils such as vegetable oils. A composition “for use as accelerator in unsaturated polyester resins” has implicitly to be at least partially soluble in the targeted resins. 
     Manganese-bearing polymers having a mean molecular weight of at least 900 Da are preferred. The mean molecular weight can be estimated from the remaining free functionalities of the polymer, or by any appropriate analytical technique such as for example GPC (Gel Permeation Chromatography) or DLS (Dynamic Light Scattering). 
     A preferred embodiment concerns a drier composition, wherein the donor ligand is one or more of the chelating ligands illustrated in  FIG.  2   , wherein the molar ratio of ligand to manganese is at least 0.005, more preferably at least 0.05. It is assumed that during drying, a fraction of the activated manganese polymers gets immobilized in the paint and is not available anymore for further catalytic reactions. 
     Preferable ratios of ligand to manganese are between 0.2 and 10, more preferably between 0.5 and 5. 
     In another preferred embodiment group X in  FIG.  1    is an ester or polyester according to  FIG.  3    (with m≥1). In another preferred embodiment group X in  FIG.  1    is a urethane or polyurethane according to  FIG.  4    (with m≥1). In another preferred embodiment group X in  FIG.  1    is an amide or polyamide according to  FIG.  5    (with m≥1). 
     Another preferred embodiment concerns a composition, wherein each R in  FIG.  3 ,  4  or  5   , is one or more group from the list comprising alkyl, alkenyl and alkynyl, comprising 1-40 C-atoms; cycloalkyl, cycloalkenyl, and cycloalkynyl, comprising 5-40 C-atoms; and aryl, comprising 6-40 C-atoms. In another embodiment one or more of each R is substituted with heteroatoms. 
     Another embodiment concerns a composition according to any of the above embodiments, having a manganese content of at least 0.1% in the polymer, preferably between 2% and 10%. Higher manganese concentrations, such as up to 20% are feasible, though this could reduce alkyd or UPR compatibility without offering any advantage over manganese polymers with a lower manganese content. 
     Another embodiment concerns a composition according to any of the above embodiments, further comprising one or more solvents, preferably selected from the list comprising white spirits, glycol ethers, alcohols, esters, aromatics, and mixtures thereof. Using such a composition is preferred, as it allows addition to target paints and varnishes in diluted form rather than in a highly viscous or solid form. 
     Another embodiment concerns a coating composition, comprising a polymer composition according to any of the above embodiments in an amount selected so as to contain 0.0005% to 0.05% of manganese. 
     Another embodiment concerns the use of the composition according to any of the above embodiments as drier for auto-oxidizable coatings or as accelerator in unsaturated polyester resins. 
     All percentages are understood to be percentages by weight. 
     Examples 1 to 22 illustrate the synthesis of polymers according to the invention. 
     EXAMPLE 1: MNP1 
     23 parts of dodecanedioic acid and 56 parts of oleic acid are heated under nitrogen blanket to 130° C. for two hours. 9 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. To facilitate removal of reaction water, xylene can be used under reflux conditions. After all water is removed, the reaction mixture is cooled to 130° C. 12.3 parts of manganese acetate are carefully added, after which the temperature is raised to 140° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. The resulting liquid manganese polymer, comprising hydrocarbon chains, esters, polyesters and a manganese content of 3.2%, is left to cool and can be diluted with white spirit to the desired concentration. 
     EXAMPLE 2: MNP2 
     35 parts of dimeric fatty acids and 35 parts of oleic acid are heated under nitrogen blanket to 130° C. 5.6 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 130° C. 7.5 parts of manganese acetate are carefully added, after which the temperature is raised to 180° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. The resulting liquid manganese polymer, comprising hydrocarbon chains, esters, polyesters and a manganese content of 2.3%, is left to cool and can be diluted with white spirit to the desired concentration. 
     EXAMPLE 3: MNP3 
     57 parts of dimeric fatty acids and 45 parts of oleic acid are heated under nitrogen blanket to 130° C. 9.1 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 130° C. 12.3 parts of manganese acetate are carefully added, after which the temperature is raised to 180° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. Then 3.4 parts of toluene di-isocyanate are added, and the reaction mix is kept stirring for two hours to allow further polymerization. The resulting manganese polymer, comprising hydrocarbon chains, esters, polyesters, urethanes, polyurethanes and a manganese content of 2.4%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 4: MNP4 
     35 parts of dimeric fatty acids and 35 parts of Tall Oil Fatty Acids are heated under nitrogen blanket to 130° C. 5.6 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 130° C. 7.5 parts of manganese acetate are carefully added, after which the temperature is raised to 180° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. The resulting manganese polymer, comprising hydrocarbon chains, esters, polyesters and a manganese content of 2.3%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 5: MNP5 
     29 parts of dimeric fatty acids and 14 parts of oleic acid are heated under nitrogen blanket to 120° C. 18.4 parts of manganese acetate are carefully added, after which the temperature is raised to 180° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. The resulting manganese polymer, comprising hydrocarbon chains and a manganese content of 8.8%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 6: MNP6 
     14 parts of adipic acid and 55 parts of dehydrated castor oil fatty acids are heated under nitrogen blanket to 130° C. 9 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 130° C. 12 parts of manganese acetate are carefully added, after which the temperature is raised to 180° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. The resulting manganese polymer, comprising hydrocarbon chains, esters, polyesters and a manganese content of 3.5%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 7: MNP7 
     35 parts of dimeric fatty acids and 34 parts of Soybean Oil Fatty Acids are heated under nitrogen blanket to 130° C. 5.7 parts of mono ethylene glycol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 130° C. 7.5 parts of manganese acetate are carefully added, after which the temperature is raised to 180° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. The resulting manganese polymer, comprising hydrocarbon chains, esters, polyesters and a manganese content of 2.3%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 8: MNP8 
     57 parts of dimeric fatty acids and 45 parts of oleic acid are heated under nitrogen blanket to 130° C. 9 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 130° C. 12.3 parts of manganese acetate are carefully added, after which the temperature is raised to 180° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. The reaction mixture is cooled to 100° C., 4.4 parts of isophorone diisocyanate are added and the reaction mix is kept stirring for two hours to allow further polymerization. The resulting manganese polymer, comprising hydrocarbon chains, esters, polyesters, urethanes, polyurethanes and a manganese content of 2.4%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 9: MNP9 
     35 parts of dimeric fatty acids and 35 parts of oleic acid are heated under nitrogen blanket to 130° C. 8.1 parts of trimethylolpropane are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 130° C. 7.5 parts of manganese acetate are carefully added, after which the temperature is raised to 180° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. The resulting manganese polymer, comprising hydrocarbon chains, esters, polyesters and a manganese content of 2.2%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 10: MNP10 
     11.5 parts of dimeric fatty acids, 4.6 parts of dodecanedioic acid, 2.9 parts of adipic acid, 11.3 parts of oleic acid, 11.2 parts of Soybean Oil Fatty Acids and 11.3 parts of dehydrated castor oil fatty acids are heated under nitrogen blanket to 130° C. 5.5 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 130° C. 7.5 parts of manganese acetate are carefully added, after which the temperature is raised to 180° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. The resulting manganese polymer, comprising hydrocarbon chains, esters, polyesters and a manganese content of 3.0%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 11: MNP11 
     35 parts of dimeric fatty acids and 35 parts of oleic acid are heated under nitrogen blanket to 130° C. 5.2 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 160° C. 0.6 parts of hexamethylenediamine are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 130° C. 7.5 parts of manganese acetate are carefully added, after which the temperature is raised to 180° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. The resulting manganese polymer, comprising hydrocarbon chains, esters, polyesters, amides, polyamides and a manganese content of 2.3%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 12: MNP12 
     35 parts of dimeric fatty acids, 17 parts of oleic acid and 18 parts of ricinoleic acid are heated under nitrogen blanket to 130° C. 3.7 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 130° C. 7.5 parts of manganese acetate are carefully added, after which the temperature is raised to 180° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. 
     The resulting manganese polymer, comprising hydrocarbon chains, esters, polyesters and a manganese content of 2.5%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 13: MNP13 
     35 parts of dimeric fatty acids and 35 parts of oleic acid are heated under nitrogen blanket to 130° C. 5.6 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 115° C. 2.2 parts of manganese oxide are carefully added, after which the temperature is raised to 180° C. Water is removed from the reaction medium by means of distillation. The resulting manganese polymer, comprising hydrocarbon chains, esters, polyesters and a manganese content of 4.4%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 14: MNP14 
     35 parts of dimeric fatty acids and 35 parts of oleic acid are heated under nitrogen blanket to 130° C. 5.2 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 160° C. 0.16 parts of polyamide (resin based on tall oil fatty acids) are carefully added after which the mixture is heated to 180° C. 
     Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 130° C. 7.5 parts of manganese acetate are carefully added, after which the temperature is raised to 180° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. The resulting manganese polymer, comprising hydrocarbon chains, esters, polyesters, polyamides and a manganese content of 2.2%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 15: MNP15 
     36.5 parts of ricinoleic acid are heated under nitrogen blanket to 130° C. 7.5 parts of manganese acetate are carefully added, after which the temperature is raised to 180° C. Acetic acid and water is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. The reaction mixture is cooled to 80° C., 1.3 parts of isophorone diisocyanate are carefully added and the reaction mix is kept stirring for four hours to allow further polymerization. The resulting manganese polymer, comprising esters, urethanes, polyesters, polyurethanes and a manganese content of 1.7%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 16: MNP16 
     28 parts of dimeric fatty acids, 2 parts of succinic add and 34 parts of dehydrated castor oil fatty acids are heated under nitrogen blanket to 130° C. 5.6 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 115° C. 2.2 parts of manganese oxide are carefully added, after which the temperature is raised to 180° C. Water is removed from the reaction medium by means of distillation. The resulting manganese polymer, comprising hydrocarbon chains, esters, polyesters and a manganese content of 2.5%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 17: MNP17 
     28 parts of dimeric fatty acids, 2 parts of itaconic acid and 34 parts of dehydrated castor oil fatty acids are heated under nitrogen blanket to 130° C. 5.6 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 115° C. 2.2 parts of manganese oxide are carefully added, after which the temperature is raised to 180° C. Water is removed from the reaction medium by means of distillation. The resulting manganese polymer, comprising hydrocarbon chains, esters, polyesters and a manganese content of 2.4%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 18: MNP18 
     29 parts of dimeric fatty acids, 3 parts of benzoic acid and 30 parts of dehydrated castor oil fatty acids are heated under nitrogen blanket to 130° C. 6 parts of mono ethylene glycol are carefully added after which the mixture is heated to 190° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 115° C. 2.2 parts of manganese oxide are carefully added, after which the temperature is raised to 180° C. Water is removed from the reaction medium by means of distillation. The resulting manganese polymer, comprising hydrocarbon chains, aromatic groups, esters, polyesters and a manganese content of 2.5%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 19: MNP19 
     70 parts of dimeric fatty acids and 68 parts of oleic acid are heated under nitrogen blanket to 130° C. 13 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 130° C. 7.5 parts of manganese acetate are carefully added, after which the temperature is raised to 180° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. The resulting liquid manganese polymer with a manganese content of 1.2%, is left to react for an additional 8 hours at 160° C. to allow further polymerization, after which it is cooled and diluted with white spirit to the desired concentration. The obtained manganese polymer, comprising hydrocarbon chains, esters and polyesters, has an average molecular weight of over 148.000 Da. 
     EXAMPLE 20: MNP20 
     34 parts of dimeric fatty acids, 2 parts of acrylic acid and 27 parts of dehydrated castor oil fatty acids are heated under nitrogen blanket to 130° C. 5.5 parts of glycerol are carefully added after which the mixture is heated to 190° C. Water is removed from the reaction medium by means of distillation. After all water is removed, the reaction mixture is cooled to 120° C. 2.2 parts of manganese oxide are carefully added, after which the temperature is raised to 180° C. Water is removed from the reaction medium by means of distillation. The resulting manganese polymer, comprising hydrocarbon chains, esters, acrylates, polyesters and a manganese content of 2.4%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 21: MNP21 
     11.5 parts of dimeric fatty acids, 4.6 parts of dodecanedioic acid, 2.9 parts of adipic acid, 11.3 parts of oleic acid, 11.2 parts of Soybean Oil Fatty Acids and 11.3 parts of dehydrated castor oil fatty acids are heated under nitrogen blanket to 130° C. 3.8 parts of manganese acetate are carefully added, after which the temperature is raised to 160° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. After all acetic acid is removed, 6.6 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. Residual water is removed by vacuum distillation. 
     To 100 parts of the resulting manganese polymer, 4 parts of a solution containing 49.9 parts methyl methacrylate, 49.9 parts butanol and 0.2 parts benzoyl peroxide, are added. The reaction temperature is raised to 70° C. Upon completion, the thick acryl-modified manganese polymer (modification at the double bonds of the fatty acid chains), comprising hydrocarbon chains, esters, acrylates, polyesters and polyacrylates, is diluted to the desired concentration. 
     EXAMPLE 22: MNP22 
     40 parts of dimeric fatty acids, 2.3 parts of dodecanedioic acid, 1.5 parts of adipic acid, and 22.4 parts of Soybean Oil Fatty Acids are heated under nitrogen blanket to 130° C. 3.8 parts of manganese acetate are carefully added, after which the temperature is raised to 160° C. Acetic acid is removed by means of distillation. Residual acetic acid is removed by vacuum distillation. After all acetic acid is removed, 6.6 parts of glycerol are carefully added after which the mixture is heated to 180° C. Water is removed from the reaction medium by means of distillation. Residual water is removed by vacuum distillation, after which 2 parts of Dow Corning RSN-6018 silicone resin intermediate is added at 180° C. and left to react for 3 hours. The resulting silicone-modified manganese polymer (silicone bonded via the residual OH— groups of the Mn polymer), comprising hydrocarbon chains, esters, polyesters and a manganese content of 1.2%, is left to cool and diluted with white spirit to the desired concentration. 
     EXAMPLE 23: PREPARATION OF CHELATED POLYMERS 
     Example 23 illustrates the preparation of driers by combining the synthesized polymers with different ligands. 
     A manganese polymer solution according to Examples 1 to 22 (MNPx) is carefully heated to 30° C., after which a donor ligand according to Table 1 (Lx) is added in a predetermined L:Mn ratio, and left to react for two hours. The Mn polymer drier (MNPx-Lx) is filtered, after which a clear reddish-brown manganese polymer solution is obtained with a manganese content of about 1% and a broad molecular weight distribution between 700 and more than 10000 Da. 
     In the general procedure above ratios of ligand to manganese (L:Mn) can range from 0.05:1 to 20:1. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Overview of the ligands 
               
            
           
           
               
               
            
               
                 Lx 
                 Product 
               
               
                   
               
               
                 L1 
                 1,4,7-Trimethyl-1,4,7-triazacyclononane 
               
               
                 L2 
                 6-isopropylamino-1,4,6-trimethyl-1,4-diazacycloheptane 
               
               
                 L3 
                 2,2′-Bipyridine 
               
               
                 L4 
                 1,10-Phenanthroline 
               
               
                 L5 
                 N,N′-Bis(salicylidene)ethylenediamine 
               
               
                 L6 
                 1,1,4,7,10,10-Hexamethyltriethylenetetramine 
               
               
                 L7 
                 Tris(2-pyridylmethyl)amine 
               
               
                 L8 
                 2-(n-benzyl-n-(2-hydroxyethyl)aminomethyl)-3-hydroxypyridine 
               
               
                 L9 
                 3-hydroxy-2-(morpholinomethyl)-pyridine 
               
               
                 L10 
                 2-(dimethylaminomethyl)-pyridine 
               
               
                 L11 
                 2-(bis-(2-pyridylmethyl)-amino)-ethanol 
               
               
                 L12 
                 1,4,6-trimethyl-6-{N-(pyridin-2-ylmethyl)-N-methylamino}-1,4- 
               
               
                   
                 diazacycloheptane 
               
               
                 L13 
                 6-amino-1,4,6-trimethyl-1,4-diazacycloheptane 
               
               
                   
               
            
           
         
       
     
     EXAMPLE 24: COATING COMPOSITION 
     Example 24 illustrates the preparation of coating compositions comprising the driers according to Example 23. 
     The drying performance of the chelated polymers prepared according to Example 23 are investigated in a white gloss alkyd-based paint formulation based on the commercially available alkyd Valirex® RE070.06. Herein, the polymer is mixed in the non-siccativated white paint together with secondary calcium- and zirconium-based driers, as commonly done in industrial practice. The mixing ratios are chosen so as to obtain a white gloss paint with a metal content of 0.005% Mn, 0.2% Ca and 0.1% Zr, calculated on resin solids, unless stated differently. Commercially available Valirex® Zr 18% and Valirex® Ca 5% are used as calcium and zirconium sources respectively. 
     For comparison purposes, reference paint compositions are prepared using commercially available metal-based driers or manganese-based polymers without ligands:
         Reference 1, using Valirex® Co 10% (Co-2-ethylhexanoate);   Reference 2, using Nuodex® DryCoat (a bridged di-nuclear non-polymeric Mn-complex);   Reference 3, using Mn acetylacetonate;   Reference 4, using Mn bipyridyl;   Reference 5, using MNPx without ligand;   Reference 6, using Valirex® Mn 10% D60+acetylacetone, with Acac:Mn=25;   Reference 7, using Valirex® Mn 10% D60+bipyridyl, with Bipy:Mn=1; and,   Reference 8, using Mn neodecanoate.       

     In these compositions, the same metal ratios are implemented, except for the Co-based paint which contains 0.05% cobalt. 
     The paint compositions are applied onto glass plates with a wet film thickness of 75 μm and checked for drying time on an Elcometer® 5300 ball type drying time recorder in a controlled climate at 20° C. and 70% relative humidity based on ASTM method D5895. Three drying stages are differentiated:
         Set-to-touch or Solvent-dry, i.e. when the stylus leaves a broad scratch-line in the paint;   Tack-free or Dust-dry, i.e. when the stylus first starts to tear the film; and,   Through-dry, i.e. when the stylus leaves no visible mark on the film.       

     To evaluate the loss-of-dry, siccativated paints are stored under ambient conditions during a period of at least 1 month, and up to 1 year, after which the drying performance is re-evaluated. 
     To evaluate yellowing, 90 μm coatings are applied onto glass plates, which were stored in the dark. The yellowing, quantified by the b* coordinate (*b-value) in the CIELAB color space model, is measured with a Minolta Chroma meter CR-200. 
     Tables 2, 3, 4, 5, 6, and 7 illustrate the results obtained using the coating compositions according to example 24. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Drying times (minutes) of different 
               
               
                 manganese polymers (L:Mn = 1) 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 Set-to- 
                 Tack- 
                 Through- 
               
               
                   
                 Paint Drier 
                 touch 
                 free 
                 dry 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Reference 1 
                 18 
                 169 
                 359 
               
               
                   
                 Reference 2 
                 14 
                 199 
                 344 
               
               
                   
                 MNP1-L1 
                 50 
                 134 
                 279 
               
               
                   
                 MNP2-L1 
                 17 
                 129 
                 395 
               
               
                   
                 MNP3-L1 
                 25 
                 156 
                 272 
               
               
                   
                 MNP4-L1 
                 34 
                 235 
                 355 
               
               
                   
                 MNP5-L1 
                 17 
                 139 
                 380 
               
               
                   
                 MNP6-L1 
                 32 
                 208 
                 340 
               
               
                   
                 MNP7-L1 
                 38 
                 183 
                 291 
               
               
                   
                 MNP8-L1 
                 17 
                 130 
                 214 
               
               
                   
                 MNP9-L1 
                 31 
                 169 
                 382 
               
               
                   
                 MNP10-L1 
                 25 
                 159 
                 390 
               
               
                   
                 MNP11-L1 
                 30 
                 164 
                 298 
               
               
                   
                 MNP12-L1 
                 28 
                 150 
                 350 
               
               
                   
                 MNP13-L1 
                 30 
                 150 
                 276 
               
               
                   
                 MNP14-L1 
                 15 
                 160 
                 377 
               
               
                   
                 MNP15-L1 
                 33 
                 164 
                 480 
               
               
                   
                 MNP16-L1 
                 10 
                 266 
                 383 
               
               
                   
                 MNP17-L1 
                 14 
                 257 
                 390 
               
               
                   
                 MNP18-L1 
                 43 
                 137 
                 254 
               
               
                   
                 MNP19-L1 
                 32 
                 160 
                 286 
               
               
                   
                 MNP20-L1 
                 36 
                 160 
                 229 
               
               
                   
                 MNP21-L1 
                 23 
                 246 
                 341 
               
               
                   
                 MNP22-L1 
                 21 
                 224 
                 292 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Drying times (minutes) of manganese polymers 
               
               
                 (L:Mn = 1) using different ligands 
               
            
           
           
               
               
               
               
            
               
                   
                 Set-to- 
                 Tack- 
                 Through- 
               
               
                 Paint Drier 
                 touch 
                 free 
                 dry 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 Reference 1 
                 18 
                 169 
                 359 
               
               
                 Reference 2 
                 14 
                 199 
                 344 
               
               
                 Reference 5 MNP2 w/o ligand 
                 41 
                 689 
                 1140  
               
               
                 MNP2-L1 
                 17 
                 129 
                 395 
               
               
                 MNP2-L2 
                 26 
                 305 
                 695 
               
               
                 MNP2-L3 
                 21 
                 170 
                 461 
               
               
                 MNP2-L4 
                 20 
                 182 
                 483 
               
               
                 MNP2-L5 
                 15 
                 182 
                 393 
               
               
                 MNP2-L6 
                 25 
                 380 
                 699 
               
               
                 MNP2-L7 
                 22 
                 117 
                 294 
               
               
                 MNP2-L8 
                 25 
                 226 
                 381 
               
               
                 MNP2-L9 
                 27 
                 333 
                 616 
               
               
                 MNP2-L10 
                 27 
                 271 
                 476 
               
               
                 MNP2-L11 
                 9 
                 244 
                 359 
               
               
                 MNP2-L12 
                 16 
                 183 
                 272 
               
               
                 MNP2-L13 
                 26 
                 320 
                 642 
               
               
                 Reference 5 MNP8 w/o ligand 
                 46 
                 None 
                 None 
               
               
                 MNP8-L1 
                 17 
                 130 
                 214 
               
               
                 MNP8-L3 
                 20 
                 250 
                 451 
               
               
                 MNP8-L5 
                 17 
                 131 
                 293 
               
               
                 MNP8-L12 
                 16 
                 182 
                 325 
               
               
                 Reference 5 MNP15 w/o ligand 
                 40 
                 None 
                 None 
               
               
                 MNP15-L1 
                 33 
                 164 
                 480 
               
               
                 MNP15-L12 
                 21 
                 181 
                 319 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 Impact of L:Mn ratio on drying times 
               
               
                 (minutes) of manganese polymers 
               
            
           
           
               
               
               
               
            
               
                   
                 Set-to- 
                 Tack- 
                 Through- 
               
               
                 Paint Drier 
                 touch 
                 free 
                 dry 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 Reference 1 
                 18 
                 169 
                 359 
               
               
                 Reference 5 MNP2 w/o ligand 
                 25 
                 689 
                 1140  
               
               
                 MNP2-L1, L1:Mn = 0.1 
                 22 
                 414 
                 732 
               
               
                 MNP2-L1, L1:Mn = 0.25 
                 17 
                 325 
                 535 
               
               
                 MNP2-L1, L1:Mn = 1.0 
                 17 
                 129 
                 395 
               
               
                 MNP2-L2, L2:Mn = 1.0 
                 26 
                 305 
                 695 
               
               
                 MNP2-L2, L2:Mn = 2.0 
                 37 
                 264 
                 487 
               
               
                 MNP2-L6, L6:Mn = 1.0 
                 25 
                 380 
                 699 
               
               
                 MNP2-L6, L6:Mn = 5.0 
                 11 
                 366 
                 600 
               
               
                 MNP2-L6, L6:Mn = 10 
                 20 
                 325 
                 475 
               
               
                 MNP2-L6, L6:Mn = 20 
                 27 
                 245 
                 414 
               
               
                 MNP2-L7, L7:Mn = 0.25 
                 16 
                 378 
                 515 
               
               
                 MNP2-L7, L7:Mn = 0.5 
                 18 
                 272 
                 341 
               
               
                 MNP2-L7, L7:Mn = 1.0 
                 22 
                 117 
                 294 
               
               
                 MNP2-L9, L9:Mn = 1.0 
                 27 
                 333 
                 616 
               
               
                 MNP2-L9, L9:Mn = 10 
                 15 
                 287 
                 442 
               
               
                 MNP2-L12, L12:Mn = 0.1 
                 18 
                 450 
                 517 
               
               
                 MNP2-L12, L12:Mn = 0.25 
                 13 
                 390 
                 473 
               
               
                 MNP2-L12, L12:Mn = 0.5 
                 13 
                 263 
                 431 
               
               
                 MNP2-L12, L12:Mn = 1.0 
                 16 
                 183 
                 272 
               
               
                 MNP2-L13, L13:Mn = 1.0 
                 26 
                 320 
                 642 
               
               
                 MNP2-L13, L13:Mn = 10 
                 26 
                 115 
                 306 
               
               
                 Reference 5 MNP15 w/o ligand 
                 40 
                 None 
                 None 
               
               
                 MNP15-L1, L1:Mn = 0.1 
                 35 
                 515 
                 720 
               
               
                 MNP15-L1, L1:Mn = 0.25 
                 39 
                 317 
                 527 
               
               
                 MNP15-L1, L1:Mn = 0.5 
                 35 
                 290 
                 430 
               
               
                 MNP15-L1, L1:Mn = 1.0 
                 33 
                 164 
                 480 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                 Impact of manganese content on drying times (minutes) 
               
            
           
           
               
               
               
               
            
               
                   
                 Set-to- 
                 Tack- 
                 Through- 
               
               
                 Paint Drier 
                 touch 
                 free 
                 dry 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 Reference 1 
                 18 
                 169 
                 359 
               
               
                 MNP1-L1 (L1:Mn = 8), 0.005% Mn 
                 17 
                 129 
                 247 
               
               
                 MNP1-L1 (L1:Mn = 8), 0.0025% Mn 
                 27 
                 145 
                 362 
               
               
                 MNP1-L1 (L1:Mn = 8), 0.002% Mn 
                 25 
                 160 
                 395 
               
               
                 MNP1-L1 (L1:Mn = 8), 0.0012% Mn 
                 31 
                 190 
                 411 
               
               
                 MNP1-L1 (L1:Mn = 8), 0.0006% Mn 
                 38 
                 298 
                 571 
               
               
                 MNP1-L1 (L1:Mn = 4), 0.0025% Mn 
                 10 
                 186 
                 393 
               
               
                 MNP1-L1 (L1:Mn = 4), 0.002% Mn 
                 11 
                 179 
                 399 
               
               
                 MNP1-L1 (L1:Mn = 4), 0.0012% Mn 
                 12 
                 226 
                 442 
               
               
                 MNP1-L1 (L1:Mn = 4), 0.0006% Mn 
                 12 
                 340 
                 669 
               
               
                   
               
            
           
         
       
     
     As can be seen from the drying data in Tables 2 and 3, the chelated manganese polymers are very active towards the oxidative drying of alkyd-based paints. Even at manganese concentrations of 0.005% on resin solids. This concentration is 10 times lower than what is typically used with cobalt, while the drying performance remains in line with that of cobalt. Some examples of manganese-based polymers even outperform the cobalt-based driers. It can also be seen that the manganese polymers without chelating nitrogen-ligands perform poorly. 
     From the results presented in Tables 4 and 5, it is apparent that the ligand to manganese ratio, and thus the extent to which manganese is activated by such nitrogen-containing ligands, has a significant impact on the drying performance. Even if the ligand to manganese ratio is very low, the drying performance significantly improves in comparison to non-chelated polymers. Depending on the polymer, the type of ligand, and the paint composition, the optimum ligand to manganese ratio can vary, though in general, higher ratios typically give enhanced drying performance. On the other hand, from an economic point of view, lower ratios are preferred. From Table 5, it can also be seen that the concentration of manganese present in the coating can be significantly decreased by increasing the ligand to manganese ratio. 
     
       
         
           
               
             
               
                 TABLE 6 
               
             
            
               
                   
               
               
                 Drying times (minutes) of manganese polymers showing the influence 
               
               
                 of storage time (L:Mn = 1, unless stated differently) 
               
            
           
           
               
               
               
               
            
               
                   
                 Set-to- 
                 Tack- 
                 Through- 
               
               
                 Paint Drier 
                 touch 
                 free 
                 dry 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 Reference 2 - Fresh 
                 14 
                 199 
                 344 
               
               
                 Reference 2 - 6 months 
                 34 
                 290 
                 558 
               
               
                 Reference 2 - 1 year 
                 20 
                 220 
                 730 
               
               
                 Reference 6 - Fresh 
                 10 
                 228 
                 338 
               
               
                 Reference 6 - 1 month 
                 10 
                 777 
                 962 
               
               
                 Reference 7 - Fresh 
                 29 
                 217 
                 407 
               
               
                 Reference 7 - 9 days 
                 29 
                 388 
                 590 
               
               
                 Reference 7 - 1 month 
                 30 
                 460 
                 681 
               
               
                 Reference 5 MNP2 w/o ligand - Fresh 
                 17 
                 689 
                 1140  
               
               
                 Reference 5 MNP2 w/o ligand - 1 month 
                 20 
                 750 
                 None 
               
               
                 MNP2-L1 - Fresh 
                 17 
                 129 
                 395 
               
               
                 MNP2-L1 - 6 months 
                 12 
                 115 
                 299 
               
               
                 MNP2-L1 - 1 year 
                 25 
                 91 
                 262 
               
               
                 MNP2-L6 (L6:Mn = 10) - Fresh 
                 20 
                 325 
                 475 
               
               
                 MNP2-L6 (L6:Mn = 10) - 6 months 
                 32 
                 303 
                 454 
               
               
                 MNP2-L7 - Fresh 
                 30 
                 143 
                 461 
               
               
                 MNP2-L7 - 7 months 
                 31 
                 107 
                 302 
               
               
                 MNP2-L11 - Fresh 
                 9 
                 244 
                 359 
               
               
                 MNP2-L11 - 7 months 
                 19 
                 215 
                 360 
               
               
                 MNP8-L1 - Fresh 
                 17 
                 130 
                 214 
               
               
                 MNP8-L1 - 9 months 
                 18 
                 170 
                 278 
               
               
                 MNP8-L12 - Fresh 
                 16 
                 182 
                 325 
               
               
                 MNP8-L12 - 9 months 
                 9 
                 171 
                 320 
               
               
                 MNP15-L1 - Fresh 
                 24 
                 155 
                 471 
               
               
                 MNP15-L1 - 1 month 
                 24 
                 153 
                 469 
               
               
                 MNP15-L1 - 5 months 
                 34 
                 175 
                 279 
               
               
                   
               
            
           
         
       
     
     As can be seen from the drying data given in Table 6, the disclosed manganese coordination polymers don&#39;t reveal any significant LOD, not even after one year of maturation. This is a remarkable advance in comparison to conventional manganese complexes, which clearly reveal a significant LOD. For example, the tested Reference 6 and 7 show pronounced LOD already after some days, indicated by prolonged tack-free and through-dry times. For Reference 2 this becomes especially visible in case of the measured through-dry time after some months. 
     As already stated above, manganese polymers without chelating ligands perform poorly as driers, but also reveal significant LOD under the same conditions, e.g. Reference 5. This is clearly not the case for their analogues with chelating ligands, e.g. examples MNP2-L1, MNP2-L6, MNP2-L7, MNP2-L11, MNP8-L1, MNP8-L12 or MNP15-L1. 
     
       
         
           
               
             
               
                 TABLE 7 
               
             
            
               
                   
               
               
                 Yellowing (*b-values) of Mn polymers (0.005% 
               
               
                 Mn) in function of time (days) 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Paint Drier 
                 1 
                 7 
                 15 
                 30 
                 53 
                 138 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Reference 1 
                 0.25 
                 −0.56 
                 −0.55 
                 −0.28 
                 −0.09 
                 1.33 
               
               
                 Reference 2 
                 −0.55 
                 −0.12 
                 0.61 
                 0.81 
                 1.18 
                 3.48 
               
               
                 MNP2-L1 
                 −0.59 
                 −0.46 
                 −0.37 
                 −0.26 
                 −0.14 
                 0.64 
               
               
                 MNP2-L7 
                 −0.65 
                 −0.27 
                 −0.16 
                 −0.05 
                 0.1 
                 1.02 
               
               
                 MNP2-L11 
                 −0.38 
                 −0.39 
                 −0.34 
                 −0.31 
                 −0.16 
                 −0.02 
               
               
                 MNP2-L12 
                 −0.59 
                 −0.44 
                 −0.47 
                 −0.40 
                 −0.37 
                 0.26 
               
               
                   
               
            
           
         
       
     
     The results for yellowing of manganese polymers in function of time as shown in Table 7 are considered very satisfactory. The low *b-values indicate that the paint coatings remain blueish-white to white. Surprisingly, the *b-value for the cobalt-containing white paint (Reference 1) is higher than that of the manganese-containing white paints after several months, indicating faster yellowing of the former. Usually, manganese tends to cause more yellowing than cobalt. Also, the bridged di-nuclear manganese complex (reference 2) shows already a significantly faster yellowing after only a few weeks as compared to the tested manganese polymers. 
     It is assumed that further yellowing reduction over prolonged time can be achieved by reducing the manganese content in the coatings. 
     EXAMPLE 25: MANGANESE LEACHING 
     The solubility of manganese in distilled water is tested according to the flask method in the OECD 105 guideline. The results are given in Table 8. 
     
       
         
           
               
             
               
                 TABLE 8 
               
             
            
               
                   
               
               
                 Fraction of manganese (%) leaching from the manganese 
               
               
                 compounds as a function of time (days) in water 
               
            
           
           
               
               
            
               
                   
                 Time submerged in water 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Paint Drier 
                 1 day 
                 2 days 
                 3 days 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Reference 2 
                 63 
                 63 
                 63 
               
               
                   
                 Reference 8 
                 22 
                 30 
                 31 
               
               
                   
                 MNP2-L1 
                 0.3 
                 0.3 
                 0.3 
               
               
                   
                 MNP3-L1 
                 0.5 
                 0.7 
                 0.8 
               
               
                   
                 MNP6-L1 
                 5 
                 5 
                 5 
               
               
                   
                 MNP7-L1 
                 0.3 
                 0.3 
                 0.3 
               
               
                   
                 MNP8-L1 
                 0.3 
                 0.3 
                 0.3 
               
               
                   
                 MNP9-L1 
                 0.5 
                 0.5 
                 0.5 
               
               
                   
                 MNP11-L1 
                 0.1 
                 0.2 
                 0.4 
               
               
                   
                 MNP12-L1 
                 0.2 
                 0.2 
                 0.2 
               
               
                   
                 MNP14-L1 
                 0.2 
                 0.3 
                 0.3 
               
               
                   
                 MNP16-L1 
                 0.6 
                 0.6 
                 0.6 
               
               
                   
                 MNP17-L1 
                 0.3 
                 0.3 
                 0.3 
               
               
                   
                 MNP18-L1 
                 0.3 
                 0.3 
                 0.3 
               
               
                   
                 MNP19-L1 
                 0.0 
                 0.0 
                 0.4 
               
               
                   
                 MNP20-L1 
                 0.1 
                 0.1 
                 0.1 
               
               
                   
                 MNP22-L1 
                 0.2 
                 0.2 
                 0.2 
               
               
                   
                   
               
            
           
         
       
     
     As can be seen in Table 8, the amount of manganese leaching from the manganese polymers into water is very low. This is in sharp contrast to the bridged di-nuclear Mn-complex (Reference 2) and Mn neodecanoate (Reference 8). Less than 10% of manganese leaching out of the manganese polymers into water is considered acceptable; less than 1% is preferred. The values for the manganese polymers are on average about 200 times lower than those of Reference 2, indicating their high stability. 
     EXAMPLE 26: UNSATURATED POLYESTER RESIN (UPR) 
     The catalytic performance of the manganese polymers made according to Example 23 is investigated in a commercially available unsaturated polyester resin, POLYLITE® 415-000 from Reichhold. Before use, all cobalt and manganese accelerators are first diluted with white spirit to 1% metal. As a peroxide initiator, Peroxan ME-50 L is used. This is a commercially available general-purpose methyl ethyl ketone peroxide from Pergan. 
     Samples of 100 g POLYLITE® 415-000 resin are promoted with 100 ppm accelerator (based on metal) and then initiated with 1% Peroxan ME-50 L. The mixture is vigorously stirred for 30 seconds, after which the gelling is monitored with a Brookfield Model DV-III Ultra Rheometer equipped with a SC4-27 spindle. 
     
       
         
           
               
             
               
                 TABLE 9 
               
             
            
               
                   
               
               
                 Gel time, peak exotherm time (minutes) and peak 
               
               
                 exotherm temperature (° C.) of unsaturated 
               
               
                 polyester resin catalyzed by manganese polymers 
               
            
           
           
               
               
               
               
            
               
                 Accelerator 
                 Gel Time 
                 Peak exotherm time 
                 Peak exotherm temp 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 Reference 1 
                 4.4 
                 10.4 
                 147 
               
               
                 MNP2-L1 
                 2.8 
                 6.2 
                 48 
               
               
                 MNP2-L11 
                 79 
                 148 
                 121 
               
               
                 MNP2-L12 
                 13.9 
                 45.2 
                 135 
               
               
                   
               
            
           
         
       
     
     Tables 9 illustrates the results obtained using the unsaturated polyester composition according to Example 26. 
     As can be seen, the disclosed manganese polymers can also be used as accelerators for unsaturated polyester resins. Changing the ligand has a significant impact on the curing rate. Both fast and delayed curing can be achieved.