High-fluidity polycarbonate copolymer, process for production highly polymerized aromatic polycarbonate resin and aromatic polycarbonate compound

Abstract

The present inventions provide a novel polycarbonate copolymer having high fluidity and high molecular weight which is formed of a structural unit derived from an aliphatic diol compound and a structural unit derived from an aromatic dihydroxy compound, having a structure represented by the formula (III): having the content of the structural unit derived from the aliphatic diol compound of 1-30 mol %, having the Q-value (280° C., 160 kg load) in the range from 0.02 to 1.0 ml/s, and having the weight average molecular weight (Mw) of 30,000 to 100,000, and an aromatic polycarbonate compound which is formed of a structural unit derived from an aromatic dihydroxy compound which is suitable for a prepolymer for producing a high fluidity polycarbonate copolymer.

What is claimed is: 
     
         1 . A high-fluidity polycarbonate copolymer satisfying the following features (a) to (d) which is substantially formed of a structural unit represented by the following general formula (I) derived from an aliphatic diol compound having aliphatic hydrocarbon groups binding to the terminal hydroxy groups and a structural unit represented by the following general formula (II): 
       
         
           
           
               
               
           
         
       
       wherein “Q” represents a hydrocarbon group having at least 3 carbon atoms which may contain an atom of a different kind; R 1 , R 2 , R 3  and R 4  each independently represent a group selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1-30 carbon atoms and an aromatic hydrocarbon group having 6-20 carbon atoms, with the proviso that at least one of R 1  and R 2  and at least one of R 3  and R 4  are each independently selected from the group consisting of a hydrogen atom and said aliphatic hydrocarbon group; “n” and “m” each independently represent an integer of 0-10 or “n” and “m” each independently represent an integer of 1-10 in the case that Q contains no aliphatic hydrocarbon groups, 
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  each independently represent a halogen atom, an alkyl group having 1-20 carbon atoms, an alkoxy group having 1-20 carbon atoms, a cycloalkyl group having 6-20 carbon atoms, an aryl group having 6-20 carbon atoms, a cycloalkoxyl group having 6-20 carbon atoms or an aryloxy group having 6-20 carbon atoms, “p” and “q” each independently represent an integer of 0-4 and X represents a single bond or a divalent organic group selected from the group consisting of the divalent organic groups represented by the following general formulas (II′): 
       
         
           
           
               
               
           
         
       
       wherein R 3  and R 4  each independently represent a hydrogen atom, an alkyl group having 1-carbon atoms or an aryl group having 6-10 carbon atoms, with the proviso that R 3  and R 4  can be linked with each other to form an aliphatic ring,
 (a) said polycarbonate copolymer has a structure represented by the following general formula (III): 
 
       
         
           
           
               
               
           
         
       
       wherein “k” represents an integer of at least 4, “i” represents an integer of at least 1, “l” represents an integer of at least 1, “k′” represents an integer of 0 or 1, R represents a linear or branched hydrocarbon group, a phenyl group which may contain a fluorine atom, or a hydrogen atom, with the proviso that at least 70% by weight of the copolymer molecules based upon the total amount of said polycarbonate copolymer molecules has “i” which is an integer of 1,
 (b) the content of the structural unit represented by the general formula (I) is 1-30 mol % and the content of the structural unit represented by the general formula (II) is 99-70 mol % based upon the total amount of the structural units constituting said polycarbonate copolymer, 
 (c) said polycarbonate copolymer has Q-value (280° C., 160 kg load) which is an index of fluidity in the range from 0.02 to 1.0 ml/s, and 
 (d) said polycarbonate copolymer has weight average molecular weight (Mw) of 30,000 to 100,000. 
 
     
     
         2 . The high-fluidity polycarbonate copolymer according to  claim 1 , which has a structural viscosity index (N-value) represented by the following mathematical formula (1) of 1.25 or less:
   [Mathematical Formula 1]       N -value=(log( Q 160)−log( Q 10))/(log 160−log 10)  (1)
   
     
     
         3 . The high-fluidity polycarbonate copolymer according to  claim 1 , wherein said Mw and Q-value satisfy the following mathematical formula (2):
   [Mathematical Formula 2]     4.61×EXP(−0.0000785×Mw)< Q (ml/s)  (2)
   
     
     
         4 . The high-fluidity polycarbonate copolymer according to  claim 1 , wherein said Mw and Q-value satisfy the following mathematical formula (3):
   [Mathematical Formula 3]     4.61×EXP(−0.0000785×Mw)< Q (ml/s)<2.30×EXP(−0.0000310×Mw)  (3)
   
     
     
         5 . The high-fluidity polycarbonate copolymer according to  claim 1 , wherein said aliphatic diol compound which derives the structural unit represented by the general formula (I) is a compound represented by the following general formula (A):
   HO—(CR 1 R 2 ) n -Q-(CR 3 R 4 ) n —OH  (A)
   
       wherein “Q” represents a hydrocarbon group having at least 3 carbon atoms which may contain an atom of a different kind; R 1 , R 2 , R 3  and R 4  each independently represent a group selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1-30 carbon atoms and an aromatic hydrocarbon group having 6-20 carbon atoms, with the proviso that at least one of R 1  and R 2  and at least one of R 3  and R 4  are each independently selected from the group consisting of a hydrogen atom and said aliphatic hydrocarbon group; “n” and “m” each independently represent an integer of 0-10 or “n” and “m” each independently represent an integer of 1-10 in the case that Q contains no aliphatic hydrocarbon groups. 
     
     
         6 . The high-fluidity polycarbonate copolymer according to  claim 5 , wherein said aliphatic diol compound is a compound represented by the following general formula (i):
   HO—(CR 1 R 2 ) n1 -Q 1 -(CR 3 R 4 ) m1 —OH  (i)
   
       wherein Q 1  represents a hydrocarbon group having 6-40 carbon atoms containing aromatic ring(s); R 1 , R 2 , R 3  and R 4  each independently represent a group selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1-30 carbon atoms and an aromatic hydrocarbon group having 6-20 carbon atoms; “n1” and “m1” each independently represent an integer of 1-10. 
     
     
         7 . The high-fluidity polycarbonate copolymer according to  claim 6 , wherein said aliphatic diol compound is selected from the group consisting of 4,4′-bis(2-hydroxyethoxy)biphenyl, 2,2′-bis[(2-hydroxyethoxy)phenyl]propane, 9,9′-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9′-bis(hydroxymethyl)fluorene, 9,9′-bis(hydroxyethyl)fluorene, fluorene glycol and fluorene diethanol. 
     
     
         8 . The high-fluidity polycarbonate copolymer according to  claim 5 , wherein said aliphatic diol compound is a compound represented by the following general formula (ii):
   HO—(CR 1 R 2 ) n2 -Q 2 -(CR 3 R 4 ) m2 —OH  (ii)
   
       wherein Q 2  represents a linear or branched hydrocarbon group having 3-40 carbon atoms which may contain heterocyclic ring(s); R 1 , R 2 , R 3  and R 4  each independently represent a group selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1-30 carbon atoms and an aromatic hydrocarbon group having 6-20 carbon atoms; “n2” and “m2” each independently represent an integer of 0-10. 
     
     
         9 . The high-fluidity polycarbonate copolymer according to  claim 8 , wherein said Q 2  represents a branched chain aliphatic hydrocarbon group having 6-40 carbon atoms which contains no heterocyclic rings. 
     
     
         10 . The high-fluidity polycarbonate copolymer according to  claim 9 , wherein said aliphatic diol compound is selected from the group consisting of 2-butyl-2-ethylpropane-1,3-diol, 2,2-diisobutylpropane-1,3-diol, 2-ethyl-2-methylpropane-1,3-diol 2,2-diethylpropane-1,3-diol and 2-methyl-2-propylpropane-1,3-diol 
     
     
         11 . The high-fluidity polycarbonate copolymer according to  claim 5 , wherein said aliphatic diol compound is a compound represented by the following general formula (iii):
   HO—(CR 1 R 2 ) n3 -Q 3 -(CR 3 R 4 ) m3 —OH  (iii)
   
       wherein Q 3  represents a cyclic hydrocarbon group having 6-40 carbon atoms; R 1 , R 2 , R 3  and R 4  each independently represent a group selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1-30 carbon atoms and an aromatic hydrocarbon group having 6-20 carbon atoms; “n3” and “m3” each independently represent an integer of 0-10. 
     
     
         12 . The high-fluidity polycarbonate copolymer according to  claim 11 , wherein said aliphatic diol compound is selected from the group consisting of pentacyclopentadecanedimethanol, 1,4-cyclohexanedimethanol, 1,3-adamantanedimethanol, decalin-2,6-dimethanol and tricyclodecanedimethanol. 
     
     
         13 . The high-fluidity polycarbonate copolymer according to  claim 5 , wherein said aliphatic diol compound has a boiling point of 240° C. or higher. 
     
     
         14 . A molded product molded by a method selected from the group consisting of injection molding, blow molding, extrusion molding, injection blow molding, rotational molding and compression molding using the high-fluidity polycarbonate copolymer according to  claim 1 . 
     
     
         15 . A molded product selected from the group consisting of a sheet product or a film product formed of the high-fluidity polycarbonate copolymer according to  claim 1 .