Polyester polyols from recycled polymers and waste streams

Abstract

The present invention relates to polyester polyols made from aromatic polyacid sources such as thermoplastic polyesters. The polyols can be made by heating a thermoplastic polyester such as virgin polyethylene terephthalate, recycled polyethylene terephthalate, or mixtures thereof, with a glycol to give a digested intermediate which is then reacted with a digestible polymer, which can be obtained from various recycle waste streams. The polyester polyols comprise a glycol-digested polyacid source and a further digestible polymer. The polyester polyols provide a sustainable alternative to petrochemical or biochemical based polyester polyols.

1 - 20 . (canceled) 
     
     
         21 . A polyester polyol comprising recurring units generated from:
 (a) an aromatic polyacid source, and   (b) a digestible polymer containing a functional group selected from an ester, amide, ether, carbonate, urea, carbamate, glycoside, and isocyanurate group, or combinations thereof.   
     
     
         22 . A polyester polyol according to  claim 21 , wherein the molar ratio of glycol to aromatic polyacid source is at least 0.8:1, and the polyol has a hydroxyl number within the range of about 10 to about 800 mg KOH/g. 
     
     
         23 . The polyester polyol according to  claim 22  having a viscosity at 125° C. less than about 5000 cP. 
     
     
         24 . A polyester polyol according to  claim 21  further comprising recurring units of a glycol. 
     
     
         25 . The polyester polyol according to  claim 24  wherein the glycol is selected from ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerol, trimethylolpropane, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, tetraethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, erythritol, pentaerythritol, sorbitol, and block or random copolymer glycols of ethylene oxide and propylene oxide, or combinations thereof. 
     
     
         26 . The polyester polyol according to  claim 24  wherein the glycol comprises a recycled glycol. 
     
     
         27 . A polyester polyol according to  21  wherein the polyacid source is other than orthophthalic acid or phthalic anhydride. 
     
     
         28 . A polyester polyol according to  claim 21  wherein,
 (a) when the polyacid source is selected from terephthalic acid, isophthalic acid, and orthophthalic acid, or esters or anhydrides thereof, or combinations of said acids, esters, or anhydrides thereof, 
 (b) the digestible polymer contains a functional group selected from an ester, amide, ether, carbonate, urea, carbamate, glycoside, and isocyanuarate group, or combinations thereof. 
 
     
     
         29 . A polyester polyol according to  claim 21  wherein,
 (a) when the polyacid source is selected from terephthalic acid, isophthalic acid, or esters thereof, or combinations of said acids or esters thereof, 
 (b) the digestible polymer contains a functional group selected from an ester, amide, ether, carbonate, urea, carbamate, glycoside, and isocyanurate group, or combinations thereof. 
 
     
     
         30 . A polyester polyol according to  claim 21  further comprising a hydrophobe or nonionic surfactant, or combinations thereof. 
     
     
         31 . A polyester polyol according to  claim 30  wherein the wherein the hydrophobe or nonionic surfactant is selected from ricinoleic acid, castor oil, ethoxylated castor oil, saturated or unsaturated C 9 -C 18  dicarboxylic acids, vegetable oils, fatty acids, fatty acid esters, modified vegetable oils, fatty triglycerides, cardanol-based products, recycled cooking oil, isostearyl alcohol, hydroxy-functional materials derived from epoxidized, ozonized, or hydroformylated fatty esters, dimer fatty acids, block copolymers of ethylene oxide with propylene oxide, alkoxylated alkyl phenols, alkoxylated fatty alcohols, or combinations thereof. 
     
     
         32 . A polyester polyol comprising recurring units from:
 (a) an aromatic polyacid source selected from phthalic acid, phthalic anhydride, dimethyl phthalates, dialkyl phthalates, terephthalic acid, dimethyl terephthalates, dialkyl terephthalate, isophthalic acid, dimethyl isophthalates, dialkyl isophthalates, dimethyl terephthalate, dimethyl terephthalate bottoms, trimellitic acid, trimellitic anhydride, trimethyl trimellitate, naphthalene dicarboxylic acid, pyromellitic anhydride, 2,5-furandicarboxylic acid, dialkyl 2,5-furandicarboxylate, pyromellitic acid, dialkyl naphthalene dicarboxylate, and mixtures thereof;   (b) a glycol; and   (c) a digestible polymer containing a functional group selected from an ester, amide, ether, carbonate, urea, carbamate, glycoside, and isocyanurate group, or combinations thereof;   wherein the molar ratio of glycol to aromatic polyacid source is at least 0.8:1, and the polyol has a hydroxyl number within the range of about 10 to about 800 mg KOH/g.   
     
     
         33 . The polyester polyol according to  claim 32  wherein the glycol is selected from ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerol, trimethylolpropane, 3-methyl-1,5-pentanedial, 1,4-cyclohexanedimethanol, diethylene glycol, tetraethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, erythritol, pentaerythritol, sorbitol, and block or random copolymer glycols of ethylene oxide and propylene oxide, or combinations thereof. 
     
     
         34 . The polyester polyol according to  claim 32  wherein the glycol comprises a recycled glycol. 
     
     
         35 . The polyester polyol according to  claim 32  having a viscosity at 125° C. less than about 5000 cP. 
     
     
         36 . A polyester polyol made by a process comprising:
 (a) heating an aromatic polyacid source selected from phthalic acid, phthalic anhydride, dimethyl phthalates, dialkyl phthalates, terephthalic acid, dimethyl terephthalates, dialkyl terephthalate, isophthalic acid, dimethyl isophthalates, dialkyl isophthalates, dimethyl terephthalate, dimethyl terephthalate bottoms, trimellitic acid, trimellitic anhydride, trimethyl trimellitate, naphthalene dicarboxylic acid, pyromellitic anhydride, 2,5-furandicarboxylic acid, dialkyl 2,5-furandicarboxylate, pyromellitic acid, dialkyl naphthalene dicarboxylate, and mixtures thereof with a glycol to give a digested intermediate; and   (b) reacting the resulting digested intermediate with a digestible polymer containing a functional group selected from an ester, amide, ether, carbonate, urea, carbamate, glycoside, and isocyanurate, or combinations thereof;   wherein the molar ratio of glycol to aromatic polyacid source is at least 0.8, and the polyol has a hydroxyl number within the range of about 10 to about 800 mg KOH/g.   
     
     
         37 . The polyester polyol according to  claim 36  wherein the glycol is selected from ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerol, trimethylolpropane, 3-methyl-1,5-pentanedial, 1,4-cyclohexanedimethanol, diethylene glycol, tetraethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, erythritol, pentaerythritol, sorbitol, and block or random copolymer glycols of ethylene oxide and propylene oxide, or combinations thereof. 
     
     
         38 . The polyester polyol according to  claim 36  wherein the glycol comprises a recycled glycol. 
     
     
         39 . The polyester polyol according to  claim 36  having a viscosity at 125° C. less than about 5000 cP.