Copolymer of olefin and unsaturated carboxylic acid or unsaturated carboxylic acid derivative

Abstract

The present invention provides a copolymer of an olefin and an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative, said copolymer being a spherical and/or spherical-like polymer. The copolymer provided by the invention exhibits a good morphology and has good prospects in industrial use.

1 . A copolymer of olefin and unsaturated carboxylic acid or unsaturated carboxylic acid derivative, comprising a spherical and/or spherical-like polymer, at least part of the spherical and/or spherical-like polymer having a cavity therein. 
     
     
         2 . The copolymer according to  claim 1 , wherein the copolymer comprises a structural unit derived from olefin and a structural unit of Formula I or a structural unit of a derivative of Formula I, 
       
         
           
           
               
               
           
         
         wherein in Formula I, L1-L3 each are independently selected from the group consisting of H and C 1 -C 30  alkyl, and L4 is C 1 -C 30  alkylene having a side group, the derivative of Formula I being a IIA, IIIA or IIB Group metal salt of Formula I, the C 1 -C 30  alkyl being optionally substituted by a substituent which is preferably one or more selected from the group consisting of halogen, C 1 -C 10  alkyl, C 1 -C 10  alkoxy, C 6 -C 10  aryl, cyano group and carboxyl; and preferably, the side group in L4 is one or more selected from the group consisting of halogen, C 6 -C 20  aryl, C 1 -C 20  alkyl and C 1 -C 20  alkoxy. 
       
     
     
         3 . The copolymer according to  claim 1 , wherein a density of the spherical and/or spherical-like polymer is 0.3000-0.8500 g/cm 3 , preferably 0.4000-0.7500 g/cm 3 , and the density is measured by using GB/T6463-2009. 
     
     
         4 . The copolymer according to  claim 1 , wherein an average particle size of the spherical and/or spherical-like polymer is 0.1-50.0 mm, preferably 0.5-20.0 mm. 
     
     
         5 . The copolymer according to  claim 1 , wherein a volume of the cavity in the spherical and/or spherical-like polymer having a cavity therein is 5-99%, preferably 30-95%, more preferably 50-90%, of a volume of the spherical and/or spherical-like polymer. 
     
     
         6 . The copolymer according to  claim 1 , wherein in the copolymer, a content of the structural unit of Formula I or the structural unit of the derivative of Formula I is 0.2-15.0 mol %, preferably 0.4-10.0 mol % . 
     
     
         7 . The copolymer according to  claim 1 , wherein a number-average molecular weight of the copolymer is 5000-200000, preferably 15000-150000. 
     
     
         8 . The copolymer according to  claim 1 , wherein in Formula I, L1 and L2 are H, L3 is selected from the group consisting of H, C 1 -C 10  alkyl or halogen-substituted C 1 -C 10  alkyl, L4 is C 1 -C 10  alkylene having a side group which is preferably one or more selected from the group consisting of halogen, C 6 -C 10  aryl, and C 1 -C 10  alkyl. 
     
     
         9 . A preparation method for the copolymer according to  claim 1 , comprising: contacting an olefin and an unsaturated carboxylic acid shown in Formula II or a derivative of the unsaturated carboxylic acid shown in Formula II with a catalyst and optionally a chain transfer agent for reaction in the presence of an alkane solvent to obtain the copolymer; 
       
         
           
           
               
               
           
         
         wherein in Formula II, definitions of L1-L4 are the same as the definitions of L1-L4 in Formula I, and 
         the catalyst comprises a main catalyst and a co-catalyst, and the main catalyst is selected from at least one metal complex shown in Formula III: 
       
       
         
           
           
               
               
           
         
         wherein in Formula III, R 9  and R 10  are identical to or different from each other, and each are independently selected from substituted or unsubstituted hydrocarbyl; R 2  and R 3  are identical to or different from each other, each are independently selected from the group consisting of H, halogen, and substituted or unsubstituted hydrocarbyl, and R 2  and R 3  optionally form a ring with each other; M is a Group VIII metal; X is one or more selected from the group consisting of halogen and C 1 -C 10  alkyl; and n is an integer that meets an M valence state. 
       
     
     
         10 . The preparation method according to  claim 9 , wherein the main catalyst is selected from at least one metal complex shown in Formula IV: 
       
         
           
           
               
               
           
         
         wherein in Formula IV, R 9 , R 10 , M, X, and n have the same definitions as those in Formula III; and R 5 -R 8  are identical to or different from each other, each independently selected from the group consisting of H, halogen, and substituted or unsubstituted C 1 -C 20  hydrocarbyl, and R 5 -R 8  optionally form a ring with each other. 
       
     
     
         11 . The preparation method according to  claim 9 , wherein in Formula IV, R 9  and R 10  each are independently selected from the group consisting of substituted or unsubstituted C 6 -C 30  aryl or substituted and unsubstituted C 7 -C 30  aralkyl; and R 5 -R 8  are identical to or different from each other, each independently selected from the group consisting of H and C 1 -C 20  hydrocarbyl, and R 5 -R 8  optionally form a ring with each other. 
     
     
         12 . The preparation method according to  claim 9 , wherein the main catalyst is selected from at least one metal complex shown in Formula V: 
       
         
           
           
               
               
           
         
         wherein in Formula V, R 1 -R 10  are identical to or different from each other, and each are independently selected from the group consisting of hydrogen, halogen, C 1 -C 24  hydrocarbyl or C 1 -C 24  hydrocarbyloxy, R 1 -R 3 , R 9 , and R 10  optionally forming a ring to each other, R 4 -R 6 , R 7 , and R 8  optionally forming a ring to each other; and M, X and n have the same definitions as those in Formula III and Formula IV. 
       
     
     
         13 . The preparation method according to  claim 12 , wherein in Formula V, R 7 -R 10  are H, and R 1 -R 6  are identical to or different from each other and each are independently selected from the group consisting of H and C 1 -C 3  alkyl. 
     
     
         14 . The preparation method according to  claim 9 , wherein the M is nickel. 
     
     
         15 . The preparation method according to  claim 9 , wherein the co-catalyst is selected from the group consisting of an organic aluminum compound and an organic boron compound; the organic aluminum compound is one or more selected from the group consisting of alkyl aluminoxane, alkylaluminum and alkylaluminum halides; and
 the organic boron compound is selected from the group consisting of aryl boron and borate.   
     
     
         16 . The preparation method according to  claim 9 , wherein a concentration of the main catalyst in a reaction system is 0.00001-100 mmol/L; when the co-catalyst is the organic aluminum compound, a molar ratio of aluminum in the co-catalyst and M in the main catalyst is (10-10000000):1; and when the co-catalyst is the organic boron compound, a molar ratio of boron in the co-catalyst and M in the main catalyst is (0.1-1000):1. 
     
     
         17 . The preparation method according to  claim 9 , wherein the chain transfer agent is one or more selected from the group consisting of aluminum alkyl, magnesium alkyl and zinc alkyl, and a molar ratio of the chain transfer agent and M in the main catalyst is (0.1-2000):1 
     
     
         18 . The preparation method according to  claim 9 , wherein a molar ratio of the unsaturated carboxylic acid shown in Formula II or the unsaturated carboxylic acid derivative shown in Formula II in the reaction system is 0.01-6000 mmol/L. 
     
     
         19 . The preparation method according to  claim 9 , wherein reaction conditions comprise: a reaction temperature in a range from −50° C. to 50° C. and a reaction time of 10-200 min. 
     
     
         20 . A foaming material comprising a copolymer according to  claim 1 .