Polyalkylene glycol chain-containing thiol polymer, thiol-modified monomer, mixture thereof, and admixture for cement

Abstract

To provide a polyalkylene glycol chain-containing thiol polymer which is excellent in various performances, particularly significantly excellent in cement dispersibility, and useful in various applications such as an admixture for cement; a thiol-modified monomer or mixture thereof, which can produce such polymer; production methods of the polymer and the monomer; and a dispersant and an admixture for cement, each including the polymer. The polyalkylene glycol chain-containing thiol polymer is a polyalkylene glycol chain-containing thiol polymer, wherein the polymer comprises a polyalkylene glycol chain and a polymer segment bonded to at least one end of the polyalkylene glycol chain with a sulfur atom-containing group therebetween, the polymer segment includes a constitutional unit derived from an unsaturated monomer component, and the unsaturated monomer component includes an unsaturated carboxylic acid monomer and an unsaturated polyalkylene glycol monomer.

1 . A thiol-modified monomer having a structure represented by the following formula (1) or (2):
   HS—R 1 —COO-(AO) n —OC—R 2 —SH  (1)
     HS—R 1 —COO-(AO) n —R 3   (2)
   in the formula,   R 1  and R 2  being the same or different and each representing an organic residue;   AO being the same or different and each representing one or more different oxyalkylene groups containing 2 to 18 carbon atoms;   n representing an average number of moles of oxyalkylene group and being an integer of 80 to 500; and   R 3  representing a hydrogen atom or an organic residue.   
     
     
         2 . The thiol-modified monomer according to  claim 1 ,
 wherein the thiol-modified monomer includes 10 to 5000 ppm by weight of an antioxidant.   
     
     
         3 . A production method of the thiol-modified monomer of  claim 1 ,
 comprising a step of esterifying a compound including a carboxyl group and a mercapto group in one molecule with a polyalkylene glycol.   
     
     
         4 . A thiol-modified monomer mixture comprising:
 a thiol-modified monomer having a structure represented by the following formula (3) and/or (4); and   a polymeric product of the thiol-modified monomer.
   HS—R 1 —CO-(AG)-OC—R 2 —SH  (3)
 
   HS—R 1 —CO-(AG)-R 3   (4)
 
   in the formula,   R 1  and R 2  being the same or different and each representing an organic residue,   AG representing an organic residue including at least one alkylene glycol group containing 2 to 18 carbon atoms, and   R 3  representing a hydrogen atom or an organic residue.   
     
     
         5 . The thiol-modified monomer mixture according to  claim 4 ,
 wherein the thiol-modified monomer represented by the formula (3) and/or (4) is obtainable by esterifying a compound including a carboxyl group or a hydroxyl group and a mercapto group in one molecule with a compound including an alkylene glycol group-containing organic residue.   
     
     
         6 . The thiol-modified monomer mixture according to  claim 4 ,
 wherein the thiol-modified monomer represented by the formula (3) is a dithiol modified product having a structure represented by the following formula (3′), and   the thiol-modified monomer represented by the formula (4) is a monothiol modified product having a structure represented by the following formula (4′):
   HS—R 1 —COO-(AO) m —OC—R 2 —SH  (3′)
 
   HS—R 1 —COO-(AO) m —R 3   (4′)
 
   in the formula,   R 1  and R 2  being the same or different and each representing an organic residue;   AO being the same or different and each representing one or more different oxyalkylene groups containing 2 to 18 carbon atoms;   m representing an average number of moles of oxyalkylene group and being integer of 10 to 500; and   R 3  representing a hydrogen atom or an organic residue.   
     
     
         7 . The thiol-modified monomer mixture according to any of  claim 4 ,
 wherein the thiol-modified monomer mixture includes 10 to 5000 ppm by weight of an antioxidant.   
     
     
         8 . An admixture for cement, comprising the thiol-modified monomer of  claim 1 . 
     
     
         9 . A production method of the thiol-modified monomer of  claim 2 ,
 comprising a step of esterifying a compound including a carboxyl group and a mercapto group in one molecule with a polyalkylene glycol.   
     
     
         10 . The thiol-modified monomer mixture according to  claim 5 ,
 wherein the thiol-modified monomer represented by the formula (3) is a dithiol modified product having a structure represented by the following formula (3′), and   the thiol-modified monomer represented by the formula (4) is a monothiol modified product having a structure represented by the following formula (4′):
   HS—R 1 —COO-(AO) m —OC—R 2 —SH  (3′)
 
   HS—R 1 —COO-(AO) m —R 3   (4′)
 
   in the formula,   R 1  and R 2  being the same or different and each representing an organic residue;   AO being the same or different and each representing one or more different oxyalkylene groups containing 2 to 18 carbon atoms;   m representing an average number of moles of oxyalkylene group and being integer of 10 to 500; and   R 3  representing a hydrogen atom or an organic residue.   
     
     
         11 . An admixture for cement, comprising the thiol-modified monomer of  claim 2 . 
     
     
         12 . An admixture for cement, comprising the thiol-modified monomer mixture of  claim 4 . 
     
     
         13 . An admixture for cement, comprising the thiol-modified monomer mixture of  claim 5 . 
     
     
         14 . An admixture for cement, comprising the thiol-modified monomer mixture of  claim 6 . 
     
     
         15 . An admixture for cement, comprising the thiol-modified monomer mixture of  claim 7 . 
     
     
         16 . An admixture for cement, comprising the thiol-modified monomer mixture of  claim 10 .