Method for producing polyether carbonate polyols

Abstract

The present invention relates to a method for producing polyether carbonate polyols, wherein: (i) in a first step, (a) carbon dioxide and propylene oxide or (b) carbon dioxide and a mixture of propylene oxide and at least one further alkylene oxide in a ratio by weight of >90:10 are attached to one or more H-functional starting substances in the presence of at least one DMC catalyst; ii) in a second step, the reaction mixture obtained from step (i) is (ii-1) first chain-lengthened with a mixture containing propylene oxide (PO) and ethylene oxide (EO) in a PO/EO ratio by weight of 90/10 to 20/80 in the presence of at least one DMC catalyst.

1 . A process for preparing polyether carbonate polyol, comprising
 (i) adding
 (a) carbon dioxide and propylene oxide or 
 (b) carbon dioxide and a mixture of propylene oxide and at least one further alkylene oxide in a weight ratio of >90:10 
 onto one or more H-functional starter substance(s) in the presence of at least one DMC catalyst, 
   (ii) a reaction mixture obtained from (i)
 (ii-1) is first chain-extended with a mixture comprising propylene oxide (PO) and ethylene oxide (EO) in a PO/EO weight ratio of 90/10 to 20/80 in the presence of at least one DMC catalyst, 
 (ii-2) then a resulting mixture is chain-extended with a mixture comprising propylene oxide (PO) and ethylene oxide (EO) in a PO/EO weight ratio of 60/40 to 2/98 in the presence of at least one DMC catalyst, and 
   (iii) polyether carbonate polyol resulting from (ii) is chain-extended with ethylene oxide or a mixture of propylene oxide (PO) and ethylene oxide (EO) in a PO/EO weight ratio of 5/95 to 0.1/99.9 in the presence of at least one DMC catalyst,   where the proportion by weight of EO in a mixture comprising PO and EO in (ii-2) is higher than the proportion by weight of EO in mixture comprising PO and EO in (ii-1).   
     
     
         2 . The process as claimed in  claim 1 , wherein, in (i),
 (α) a H-functional starter substance or a mixture of at least two H-functional starter substances and/or a suspension medium is initially charged and any water and/or other volatile compounds are removed by elevated temperature and/or reduced pressure comprising drying, with addition of the DMC catalyst to the H-functional starter substance and/or to the mixture of at least two H-functional starter substances and/or the suspension medium before or after the drying,   (β) activation is accomplished by adding a portion (based on the total amount of the amount of alkylene oxides used in the activation and copolymerization) of alkylene oxide selected from the group consisting of
 (a) propylene oxide and 
 (b) a mixture of propylene oxide and at least one further alkylene oxide in a weight ratio of >90:10 
 to a mixture resulting from (α), wherein said adding a portion of alkylene oxide can be effected in optional presence of CO 2 , in which case a temperature peak comprising a hotspot which occurs because of an exothermic chemical reaction that follows and/or a pressure drop in the reactor can occur, and where (β) for activation can also be effected repeatedly, 
   (γ) adding propylene oxide or a mixture of propylene oxide and at least one further alkylene oxide in a weight ratio of >90:10, carbon dioxide and optionally one or more H-functional starter substance(s) to a mixture resulting from (β), where the one or more alkylene oxides used in (γ) may be the same as or different than the one or more alkylene oxides used in (β), where at least one H-functional starter substance is added in at least one of steps (α) and (γ).   
     
     
         3 . The process as claimed in  claim 1 , wherein one or more H-functional starter substances used in (i) are one or more compounds selected from the group consisting of ethylene glycol, propylene glycol, propane-1,3-diol, butane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, 2-methylpropane-1,3-diol, neopentyl glycol, hexane-1,6-diol, octane-1,8-diol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and polyether polyols having a molecular weight Mn in a range from 150 to 4500 g/mol and a functionality of 2 to 3. 
     
     
         4 . The process as claimed in  claim 1 , wherein a reaction mixture obtained from (i)
 (ii-1) is first chain-extended with a mixture comprising propylene oxide (PO) and ethylene oxide (EO) in a PO/EO weight ratio of 80/20 to 30/70 in the presence of at least one DMC catalyst, and   (ii-2) then a resulting mixture is chain-extended with a mixture comprising propylene oxide (PO) and ethylene oxide (EO) in a PO/EO weight ratio of 40/60 to 5/95 in the presence of at least one DMC catalyst.   
     
     
         5 . The process as claimed in  claim 1 , wherein a suspension media is used and comprises 4-methyl-2-oxo-1,3-dioxolane, 1,3-dioxolan-2-one, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene and/or a mixture thereof. 
     
     
         6 . The process as claimed in  claim 1 , wherein (ii-1) and/or (ii-2) are repeated two to ten times. 
     
     
         7 . The process as claimed in  claim 6 , wherein the proportion by weight of EO increases on each repetition of (ii-1) and/or (ii-2). 
     
     
         8 . The process as claimed in  claim 1 , wherein the proportion by weight of EO in the mixture of PO and EO is increased continuously between a starting PO/EO mixing ratio and a final PO/EO mixing ratio, the starting PO/EO mixing ratio corresponding to a PO/EO weight ratio from the weight ratio defined for (ii-1), and the final PO/EO mixing ratio corresponding to a PO/EO weight ratio from the weight ratio defined for (ii-2). 
     
     
         9 . The process as claimed in  claim 1 , wherein a mean length of mixed blocks of PO and EO prepared in (ii-1) or (ii-2) is 1.0 to 20.0 alkylene oxide units, based in each case on one OH group of the polyether carbonate polyol. 
     
     
         10 . The process as claimed in  claim 1 , wherein (ii) is performed by adding a solvent not containing any H-functional groups to a reaction mixture obtained from (i). 
     
     
         11 . The process as claimed in  claim 1 , wherein a mean length of an alkylene oxide block prepared in (iii) is 1 to 30 alkylene oxide units, based in each case on one OH group of the polyether carbonate polyol. 
     
     
         12 . A polyether carbonate polyol obtainable according to  claim 1 . 
     
     
         13 . A process for producing one or more flexible polyurethane foams, comprising using a polyol component A comprising a polyether carbonate polyol obtainable according to  claim 1 . 
     
     
         14 . A process for producing one or more flexible polyurethane foams having an apparent density to DIN EN ISO 3386-1-98 in a range from ≧10 kg/m 3  to ≦150 kg/m 3  and an indentation hardness to DIN EN ISO 3386-1-98 in a range from ≧0.5 kPa to ≦20 kPa (at 40% deformation and 4th cycle) comprising reacting
 component A comprising 
 A1 100 to 10 parts by weight (based on the sum total of the parts by weight of components A1 and A2) of polyether carbonate polyol obtainable according to  claim 1 , 
 A2 0 to 90 parts by weight (based on the sum total of the parts by weight of components A1 and A2) of conventional polyether polyol, 
 A3 0.5 to 25 parts by weight (based on the sum total of the parts by weight of components A1 and A2) of water and/or physical blowing agents, 
 A4 0.05 to 10 parts by weight (based on the sum total of the parts by weight of components A1 and A2) of one or more auxiliaries and additives optionally comprising one or more
 d) catalysts, 
 e) surface-active additives, 
 f) pigments or flame retardants, 
 
 A5 0 to 10 parts by weight (based on the sum total of the parts by weight of components A1 and A2) of one or more compounds having one or more hydrogen atoms reactive toward isocyanates and having a molecular weight of 62-399, 
 with component B comprising one or more polyisocyanates, 
 where the process is effected at an index of 50 to 250, and where parts by weight of components A1 to A5 are normalized such that the sum total of the parts by weight of components A1+A2 in said component A adds up to 100. 
 
     
     
         15 . A flexible polyurethane foam having an apparent density to DIN EN ISO 3386-1-98 in a range from ≧10 kg/m 3  to ≦150 kg/m 3  and an indentation hardness to DIN EN ISO 3386-1-98 in a range from ≧0.5 kPa to ≦20 kPa (at 40% deformation and 4th cycle) obtainable by a process as claimed in  claim 13 .