High stress thermal plastic polyurethane, its preparing formulation and making process

Abstract

A high stress thermal plastic polyurethane, its preparing formulation and making process are disclosed. In particular, the high stress thermal plastic polyurethane is prepared from a formulation comprises a polycarbonate derivative and has a stress more than 2.5 MPa.

What is claimed is: 
     
         1 . A formulation for preparing thermal plastic polyurethane with high stress, comprising a first part which comprises polyurethane oligomer and a second part which comprises a chain extender; wherein the polyurethane oligomer is formed by reacting a polycarbonate derivative or a bisphenol with a diisocyanate, and wherein the polycarbonate derivative has a structure as shown in formula (1); 
       
         
           
           
               
               
           
         
         where R 1  is derived from an aliphatic diamine, an aromatic diamine or a polyether diamine, and the diisocyanate is an aromatic diisocyanate or an aliphatic diisocyanate; and wherein the chain extender is selected from one of group consisting of an aliphatic diol, a polyether diol, a polyester diol and a bisphenol; and a weight ratio of the chain extender and the polyurethane oligomer is 1-3, and m is an integer of 0-5; or 
         where R 1  is derived from an amino compound containing siloxane groups; and the diisocyanate is an aliphatic diisocyanate; and wherein the chain extender is selected from one of group consisting of an aliphatic diol and a bisphenol; and a weight ratio of the chain extender and the polyurethane oligomer is 0.2-0.8, and m is an integer of 0-5. 
       
     
     
         2 . The formulation for preparing thermal plastic polyurethane with high stress of  claim 1 , wherein the aliphatic diamine comprises a C2-C40 linear chain aliphatic diamine or a C2-C40 branched chain aliphatic diamine. 
     
     
         3 . The formulation for preparing thermal plastic polyurethane with high stress of  claim 1 , wherein the aromatic diisocyanate comprises 4,4′-methylene diphenyl diisocyanate, 4,4′-difluoromethylene diphenyl diisocyanate, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,2-phenylene diisocyanate, 2,2′-biphenyl diisocyanate, 3,3′-biphenyl diisocyanate, 4,4′-biphenyl diisocyanate, 1,5-naphthalene diisocyanate or their combination. 
     
     
         4 . The formulation for preparing thermal plastic polyurethane with high stress of  claim 1 , wherein the aliphatic diisocyanate comprises hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate or their combination. 
     
     
         5 . The formulation for preparing thermal plastic polyurethane with high stress of  claim 1 , wherein the aliphatic diol comprises a C2-C40 linear chain aliphatic diol or a C2-C40 branched chain aliphatic diol. 
     
     
         6 . The formulation for preparing thermal plastic polyurethane with high stress of  claim 1 , wherein the polyether diol is selected from one of the group consisting of polytetramethylene ether glycol, polytetramethylene ether glycol-ethylene glycol copolymer, polytetramethylene ether glycol-propylene glycol copolymer and their combination. 
     
     
         7 . The formulation for preparing thermal plastic polyurethane with high stress of  claim 1 , wherein the polyester diol comprises polycarbonate diol, polycaprolactone diol or their combination. 
     
     
         8 . The formulation for preparing thermal plastic polyurethane with high stress of  claim 1 , wherein the polyether diamine has a weight-average molecular weight between 100 and 5,000 Da. 
     
     
         9 . The formulation for preparing thermal plastic polyurethane with high stress of  claim 1 , wherein the amino compound containing siloxane groups has a molecular weight between 150 and 10,000 Da. 
     
     
         10 . The formulation for preparing thermal plastic polyurethane with high stress of  claim 1 , wherein the polyurethane oligomer has peaks at 1.35-1.65 ppm or 3.65-4.15 ppm in  1 H-NMR spectrum. 
     
     
         11 . The formulation for preparing thermal plastic polyurethane with high stress of  claim 1 , wherein the polyurethane oligomer has a weight-average molecular weight between 4,000 and 40,000 Da. 
     
     
         12 . The formulation for preparing thermal plastic polyurethane with high stress of  claim 1 , being used for preparing a thermal plastic polyurethane with stress more than about 2.5 MPa. 
     
     
         13 . A thermal plastic polyurethane, being a high stress thermal plastic polyurethane and formed by reacting a polyurethane oligomer with a diol, wherein the polyurethane oligomer has a structure as shown in formula (2): 
       
         
           
           
               
               
           
         
         when m is 0, the polyurethane oligomer is formed by reacting a bisphenol compound with a diisocyanate, and x is an integer of 5-100; or 
         when R 1  is derived from an aliphatic diamine, an aromatic diamine or a polyether diamine, and R 2  is derived from an aromatic diisocyanate or a aliphatic diisocyanate; and wherein the diol is selected from one of group consisting of a aliphatic diol, a polyether diol, a polyester diol and a bisphenol; and a weight ratio of the diol and the polyurethane oligomer is 1-3, m is an integer of 0-5, and x is an integer of 5-100; or 
         when R 1  is derived from an amino compound containing siloxane groups; and R 2  is derived from aliphatic diisocyanate; and wherein the diol is selected from one of group consisting of a aliphatic diol and a bisphenol; and a weight ratio of the diol and the polyurethane oligomer is 0.2-0.8, m is an integer of 0-5, and x is an integer of 5-100. 
       
     
     
         14 . The thermal plastic polyurethane of  claim 13 , wherein the high stress thermal plastic polyurethane has a stress more than about 2.5 MPa. 
     
     
         15 . The thermal plastic polyurethane of  claim 13 , wherein the high stress thermal plastic polyurethane has a weight-average molecular weight of 10,000-400,000 Da. 
     
     
         16 . The thermal plastic polyurethane of  claim 13 , wherein the high stress thermal plastic polyurethane has peaks at about 1.35-1.65 ppm or 3.65-4.15 ppm in  1 H-NMR spectrum. 
     
     
         17 . The thermal plastic polyurethane of  claim 13 , wherein the polyurethane oligomer has a weight-average molecular weight between 4,000 and 40,000 Da. 
     
     
         18 . The thermal plastic polyurethane of  claim 13 , wherein the aliphatic diamine comprises a C2-C40 linear chain aliphatic diamine or a C2-C40 branched chain aliphatic diamine. 
     
     
         19 . The thermal plastic polyurethane of  claim 13 , wherein the aromatic diisocyanate comprises 4,4′-methylene diphenyl diisocyanate, 4,4′-difluoromethylene diphenyl diisocyanate, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,2-phenylene diisocyanate, 2,2′-biphenyl diisocyanate, 3,3′-biphenyl diisocyanate, 4,4′-biphenyl diisocyanate, 1,5-naphthalene diisocyanate or their combination. 
     
     
         20 . The thermal plastic polyurethane of  claim 13 , wherein the aliphatic diisocyanate comprises hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate or their combination. 
     
     
         21 . The thermal plastic polyurethane of  claim 13 , wherein the aliphatic diol comprises a C2-C40 linear chain aliphatic diol or a C2-C40 branched chain aliphatic diol. 
     
     
         22 . The thermal plastic polyurethane of  claim 13 , wherein the polyether diol is selected from one of the group consisting of polytetramethylene ether glycol, polytetramethylene ether glycol-ethylene glycol copolymer, polytetramethylene ether glycol-propylene glycol copolymer and their combination. 
     
     
         23 . The thermal plastic polyurethane of  claim 13 , wherein the polyester diol comprises polycarbonate diol, polycaprolactone diol or their combination. 
     
     
         24 . The thermal plastic polyurethane of  claim 13 , wherein the polyether diamine has a weight-average molecular weight between 100 and 5,000 Da. 
     
     
         25 . The thermal plastic polyurethane of  claim 13 , wherein the amino compound containing siloxane groups has a molecular weight between 150 and 10,000 Da. 
     
     
         26 . A process for making thermal plastic polyurethane with high stress, comprising: (1) providing the formulation according to  claim 1 ; and (2) performing a chain extension reaction to have the formulation according to  claim 1  form thermal plastic polyurethane with high stress, wherein the thermal plastic polyurethane with high stress has a stress more than about 2.5 MPa. 
     
     
         27 . The process for making thermal plastic polyurethane with high stress of  claim 26 , wherein the chain extension reaction is performed between 60 and 100° C. 
     
     
         28 . The process for making thermal plastic polyurethane with high stress of  claim 26 , wherein the thermal plastic polyurethane with high stress has peaks at about 1.35-1.65 ppm or 3.65-4.15 ppm in  1 H-NMR spectrum. 
     
     
         29 . The process for making thermal plastic polyurethane with high stress of  claim 26 , wherein the thermal plastic polyurethane with high stress has a weight-average molecular weight of 10,000-400,000 Da.