Polymers, processes, compositions & uses

Abstract

The invention relates to a polymer comprising certain specific units. The invention further relates to processes for making the polymer of the invention. The invention further relates to a binder and compositions comprising the polymer, preferably to compositions suitable for paints and coatings. The invention relates in particular to water-borne, solvent-borne and powder coating compositions and preferably to curable water-borne, curable solvent-borne and curable powder coating compositions. The invention further relates to cured compositions. The invention further relates to objects, in particular coatings prepared from the compositions of the invention. The invention further relates to processes for making the compositions of the invention. The invention further relates to articles having coated thereon the compositions of the invention. The invention further relates to articles having coated and cured thereon the compositions of the invention. The invention further relates to various uses of the polymer of the invention, the binder of the invention, the composition of the invention, the cured composition of the invention and various uses of articles having coated and optionally cured thereon the compositions of the invention.

1 . A polymer comprising one or more units selected from the group consisting of S1, S2, S3 S4, and combinations thereof, wherein each of S1, S2, S3, and S4 is represented by the following corresponding formula: 
       
         
           
           
               
               
           
         
         wherein
 i) k is an integer equal to or higher than 0, and 
 ii) m is an integer equal to or higher than 0, and 
 iii) n is an integer equal to or higher than 0, and 
 iv) p is an integer equal to or higher than 0, and 
 v) the sum of k, m, n and p is equal to or higher than 1, and 
 vi) X is selected from the group consisting of L4, L6, L7, L8, L9, L10, L11, L12, L13, L20, L23, L24, L25, L26, L27, L28, and L31 as each of L4 to L31 is defined below, and wherein the black bold dots shown in the formulae of any one of L4 to L31 represent the attachment points of each of L4 to L31 to the S 1, and wherein the attachment points are carbon atoms, 
 vii) Y is selected from the group consisting of L4, L6, L7, L8, L9, L10, L11, L12, L13, L20, L23, L24, L25, L26, L27, L28, and L31 as each of L4 to L31 is defined below, and wherein the black bold dots shown in the formulae of any one of L4 to L31 represent the attachment points of each of L4 to L31 to the S2, and wherein the attachment points are carbon atoms, 
 viii) Z is selected from the group consisting of L4, L6, L7, L8, L9, L10, L11, L12, L13, L20, L23, L24, L25, L26, L27, L28, and L31 as each of L4 to L31 is defined below, and wherein the black bold dots shown in the formulae of any one of L4 to L31 represent the attachment points of each of L4 to L31 to the S3, and wherein the attachment points are carbon atoms, 
 ix) T is selected from the group consisting of L4, L6, L7, L8, L9, L10, L11, L12, L13, L20, L23, L24, L25, L26, L27, L28, and L31 as each of L4 to L31 is defined below, and wherein the black bold dots shown in the formulae of any one of L4 to L31 represent the attachment points of each of L4 to L31 to the S4, and wherein the attachment points are carbon atoms, 
 
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein 
         R 1 ″, R 2 ″ is independently selected from the group consisting of H and CH 3 , and 
         R 3 ″, is a CH 2  or C 2 -C 34  optionally-substituted-hydrocarbylene, and 
         R 12 ″ is C 4 -C 34  unsaturated-acyclic-hydrocarbyl. 
       
     
     
         2 . The polymer according to  claim 1 , wherein the polymer has a MRQ of at least 1 and at most 10, and wherein the MRQ is 
       
         
           
             
               MRQ 
               = 
               
                 
                   
                     S 
                     total 
                   
                   
                     S 
                     specific 
                   
                 
                 = 
                 
                   
                     
                       S 
                       specific 
                     
                     + 
                     
                       S 
                       rest 
                     
                   
                   
                     S 
                     specific 
                   
                 
               
             
           
         
         wherein 
         S total =S specific +S rest , and 
         S specific =(total moles S1)+(total moles S2)+(total moles S3)+(total moles S4), and 
         S rest =the total moles of all the units of a polymer wherein said units are not any one of S1, S2, S3, S4, and 
         wherein the MRQ is determined is determined via NMR spectroscopy, as described in the description. 
       
     
     
         3 . The polymer according to  claim 2 , wherein the polymer has a MRQ of at most 4. 
     
     
         4 . The polymer according to  claim 2 , wherein the polymer has a MRQ of at most 1.4, preferably at most 1.3. 
     
     
         5 . The polymer according to  claim 1  wherein the polymer has:
 i) a number average molecular weight (M n ) of at least 10 3  and at most 5×10 4 , Da, and 
 ii) a polydispersity D (=M w /M n ) of at least 1.1 and at most 5, and 
 iii) a glass transition temperature (T g ) of at least −25 and at most 150° C., and 
 iv) an acid value (AV) of at least 10 and at most 350 mg KOH/g, and 
 v) a hydroxyl value (OHV) of at least 0 and at most 350 mg KOH/g, and 
 vi) a functionality (f) of at least 0.2 and at most 50, 
 wherein 
 M w  is the weight average weight and is measured via Gel Permeation Chromatography according to the description, and 
 M n  is measured via Gel Permeation Chromatography according to the description, and 
 T g  is measured via Differential Scanning Calorimetry according to the description, and 
 AV is measured titrimetrically via ISO 2114, and 
 OHV is measured titrimetrically via ISO 4629, and 
 f is as defined and measured in the description. 
 
     
     
         6 . The polymer according to  claim 1  wherein the polymer has:
 i) a number average molecular weight (M n ) of at least 8×10 2  and at most 10 4 , Da, and 
 ii) a polydispersity (D) (D=M w /M n ) of at least 1.1 and at most 4, and 
 iii) a glass transition temperature (T g ) of at least 20 and at most 150° C., and 
 iv) an acid value (AV) of at least 20 and at most 350 mg KOH/g, and 
 v) a hydroxyl value (OHV) of at least 0 and at most 400 mg KOH/g, and 
 vi) a functionality (f) of at least 3 and at most 25, 
 wherein 
 M w  is the weight average weight and is measured via Gel Permeation Chromatography according to the description, and 
 M n  is measured via Gel Permeation Chromatography according to the description, and 
 T g  is measured via Differential Scanning Calorimetry according to the description, and 
 AV is measured titrimetrically via ISO 2114, and 
 OHV is measured titrimetrically via ISO 4629, and 
 f is as defined and measured in the description. 
 
     
     
         7 . The polymer according to  claim 1 , wherein the polymer is ionic. 
     
     
         8 . A process for making a polymer as defined in  claim 1  comprising the steps of:
 a. providing:
 a-i) a mono-epoxide selected from the group consisting of E4, E6, E7, E8, E9, E10, E11, E12, E13, E20, E23, E24, E25, E26, E27, E28, E31 and mixtures thereof, as each of E4 to E31 is represented by the following corresponding formula: 
 
 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein 
         R 1 ″′, R 2 ″′ is independently selected from the group consisting of H and CH 3 , and 
         R 3 ′″, is a CH 2  or C 2 -C 34  optionally-substituted-hydrocarbylene, and 
         R 12 ′″ is C 4 -C 34  unsaturated-acyclic-hydrocarbyl, 
         and wherein none of R 1 ′″, R 2 ′″, R 3 ′″, R 12 ′″ comprises any anhydride group, and
 a-ii) a reagent A selected from the group consisting of trimellitic acid anhydride, trimellitic acid, citric acid anhydride, citric acid and mixtures thereof, and 
 a-iii) optionally a catalyst A, and 
 a-iv) optionally an organic solvent, and 
 a-v) optionally a reagent B selected from the group comprising of anhydride A, cyclic ester and mixtures thereof, 
 
         and 
         b. charging a-i) to a-v) provided in step a. into a reaction vessel to form a reaction mixture, and 
         c. polymerizing the reaction mixture,
 c-i) at a temperature of at least 60 and at most 200° C., and 
 c-ii) for a time of at least 0.5 hours and at most 200 hours, and 
 c-iii) removing water by applying vacuum, if water is formed during the polymerization of the reaction mixture, and 
 c-iv) optionally applying pressure with the proviso that vacuum and pressure are not applied at the same time, 
 
         to afford the polymer, 
         and 
         d. discharging the polymer from the reaction vessel and collecting said polymer, 
         and wherein 
         the molar ratio L between the moles of monoepoxide as defined in a-i) and the moles of reagent A as defined in a-ii),
 Molar ratio L=moles of monoepoxide/moles of reagent A 
 
         is at least 0.1 and at most 2.9, preferably at least 0.3 and at most 2.8. 
       
     
     
         9 . A composition comprising a binder, wherein the binder comprises:
 i) a polymer according to  claim 1 , and   ii) a constituent A selected from the group consisting of organic metal salt, thermal initiator, photoinitiator, copolymerizable agent and mixtures thereof.   
     
     
         10 . The composition according to  claim 9 , wherein the composition is liquid at room temperature and atmospheric pressure. 
     
     
         11 . The composition according to  claim 9 , wherein the composition is solid at room temperature and atmospheric pressure. 
     
     
         12 . The composition according to  claim 9 , wherein the composition is a coating composition selected from the group consisting of water-borne coating composition, solvent-borne coating composition and powder coating composition. 
     
     
         13 . The composition according to  claim 9 , wherein the composition is a coating composition selected from the group consisting of water-borne coating composition, solvent-borne coating composition. 
     
     
         14 . A cured composition as the composition is defined in  claim 9 . 
     
     
         15 . An article having coated a composition as the composition is defined in  claim 9 . 
     
     
         16 . An article having coated and cured thereon a composition as the composition is defined in  claim 9 . 
     
     
         17 . (canceled) 
     
     
         18 . A product which comprises the polymer according to  claim 1 , wherein the product is selected from the group consisting of in paints, polishes, inks, adhesives, pastes, 3D-printing, automotive products, marine products, aerospace products, medical products, defense products, sports/recreational products, architectural products, bottling products, household products, machinery products, can products, coil products, energy products, textiles and electrical products.