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US 2019 / 0256450 A1 ESSADDAM Et Al US 20190256450A1 ( 19) United States (12 ) Patent Application Publication ( 10) Pub . No. : US 2019 / 0256450 A1 ESSADDAM et al. (43 ) Pub. Date : Aug . 22 , 2019 ( 54 ) TEREPHTHALIC ACID ESTERS C08J 7 / 02 (2006 .01 ) FORMATION C08 ) 11 / 24 (2006 .01 ) C07C 29 / 09 ( 2006 .01 ) (71 ) Applicant : 9449710 CANADA INC ., Terrebonne C08J 11 / 26 ( 2006 .01 ) (CA ) C08K 5 / 05 ( 2006 . 01 ) C07C 31 / 20 ( 2006 .01 ) (72 ) Inventors: Adel ESSADDAM , Sherbrooke (CA ) ; C07C 51 /09 ( 2006 .01 ) Fares ESSADDAM , Sainte - Therese CO8L 67703 (2006 . 01 ) ( CA ) (52 ) U . S . CI. CPC .. .. .. .. .. C07C 69 /82 ( 2013 . 01 ) ; C08F 8 /50 (21 ) Appl. No. : 16 /259 , 980 ( 2013 .01 ) ; C07C 29 / 1285 ( 2013 . 01 ) ; C07C 67 /08 (2013 .01 ) ; C08J 7 / 02 ( 2013 .01 ) ; C08J (22 ) Filed : Jan . 28 , 2019 11 /24 (2013 . 01) ; C08J 2367/ 03 (2013 . 01 ) ; C08J 11/ 26 ( 2013 .01 ) ; C08K 5 /05 ( 2013 . 01 ) ; Related U . S . Application Data C07C 31/ 202 (2013 .01 ) ; C07C 51/ 09 (63 ) Continuation of application No . 15/ 706 , 484 , filed on ( 2013 .01 ) ; C08L 67/ 03 ( 2013. 01 ) ; C07C Sep . 15 , 2017 , now Pat . No . 10 , 252, 976 . 29 /095 (2013 . 01 ) Publication Classification (57 ) ABSTRACT (51 ) Int. Ci. The present disclosure relates to the formation of terephtha C07C 69 /82 ( 2006 .01 ) late esters . The present invention also relates to the depo CO8F 8 /50 ( 2006 .01 ) lymerization of polyethylene terephthalate (PET ) or poly C07C 29 / 128 ( 2006 . 01 ) ( ethylene glycol - co - 1 , 4 - cyclohexanedimethanol C07C 67 /08 ( 2006 .01 ) terephthalate ) and the recovery of terephthalate esters US 2019 / 0256450 A1 Aug . 22 , 2019 TEREPHTHALIC ACID ESTERS [ 0012 ] (c ) a sub - stoichiometric amount of an alkox FORMATION ide . [ 0013 ] In some embodiments , R or R² is methyl . CROSS -REFERENCE TO RELATED [0014 ]. In some embodiments , the alcoholic solvent is APPLICATION selected from methanol, ethanol, n -propanol , isopropanol, t -butanol , ethylene glycol, glycerol, cyclohexane - 1 , 4 - di [0001 ] This application is a continuation application yldimethanol, phenol, benzyl alcohol, and any combinations which claims the benefit of priority from U . S . patent appli thereof . cation Ser. No . 15 /706 ,484 , filed Sep . 15 , 2017 . [0015 ] In some embodiments , the alcoholic solvent is methanol. FIELD OF THE INVENTION [ 0016 ] In some embodiments , the solvent for swelling the [ 0002 ] The present disclosure relates to the formation of polyester is selected from a non polar solvent, a polar aprotic ester derivatives from polyesters and more specifically to the solvent, a polar protic solvent, and any combinations formation of terephthalic acid esters from polyethylene thereof. terephthalate (PET ) or poly ( ethylene glycol- co - 1 , 4 -cyclo [0017 ] In some embodiments , the solvent for swelling the hexanedimethanol terephthalate ) (PETG ) . The present dis polyester is selected from DMSO , DMF, acetone , a haloge closure also relates to the formation of dimethyl terephtha nated solvent, n - hexane, nitrobenzene , methanol , benzyl late (DMT ) . alcohol, benzaldehyde , and any combinations thereof. 10018 ] In some embodiments , the solvent for swelling the BACKGROUND OF THE INVENTION polyester is a halogenated solvent. [0019 ] In some embodiments , the ratio of solvent for [ 0003 ] The polyethylene terephthalate (PET ) bottle resin swelling the polyester to alcoholic solvent is between about market has been growing strongly as PET resins have 0 . 1 : 1 and about 2 : 1 (wow ) . replaced glass in carbonated soft drink , bottled water and [0020 ] In some embodiments , the ratio of solvent for food containers . swelling the polyester to alcoholic solvent is between about [ 00041 Dimethyl terephthalate (DMT ) is primarily used in 0 . 5 : 1 and about 1 : 1 ( w : w ) . the manufacture of polyethylene terephthalate (PET ) for 10021 ] In some embodiments , the alkoxide is selected fiber , film , container plastics, and specialty plastics applica from an alkali metal alkoxide , an alkaline earth metal tions. alkoxide , a metal alkoxide , an ammonium alkoxide and any 100051 The largest polyester sector is the fibers market combinations thereof. where it is used to make clothes, home textiles such as sheets 10022 ]. In some embodiments , the alkoxide is generated and curtains, carpets and rugs, and industrial products such in - situ by addition of an alkali metal , an alkaline earth metal , as tire cord , seat belts , hoses and ropes . PET film is utilized or a metal to the alcoholic solvent . in electrical applications such as dielectric metal foil capaci [0023 ] In some embodiments , the ratio of polyester to tors and for food packaging . alkoxide is between about 15 : 1 and about 125 : 1 ( w : w ) . [ 0006 ] The growth in polyester has not been converted [ 0024 ] In some embodiments , the ratio of polyester to into DMT demand . For most grades of polyester used in alkoxide is between about 20 : 1 and about 25 : 1 ( w : W ) . textiles and food and beverage containers , it is more eco [0025 ] In some embodiments , the admixing of the poly nomical to use purified terephthalic acid rather than DMT. ester with the solvent for swelling the polyester, the alkox ide , and the alcoholic solvent is performed until an about SUMMARY OF THE INVENTION 80 % yield of the terephthalate of Formula ( I ) is achieved . [ 0007 ] Disclosed herein is a process for the transformation 10026 ] In some embodiments , the admixing of the poly of a polyester selected from polyethylene terephthalate and ester with the solvent for swelling the polyester , the alkox poly ( ethylene glycol- co - 1 , 4 - cyclohexanedimethanol ide , and the alcoholic solvent is performed without external terephthalate ) into a terephthalate of Formula ( I) : heat. [ 0027 ] In some embodiments , the admixing of the poly ester with the solvent for swelling the polyester , the alkox Formula ( I) ide , and the alcoholic solvent is performed at atmospheric pressure . [ 0028 ] Also disclosed herein is a process for the transfor mation of polyethylene terephthalate into dimethyl R1 - 0 0 - R2; terephthalate , comprising admixing the polyethylene terephthalate with a mixture comprising: [ 0008 ] wherein Rl and R2 are independently selected [0029 ] ( a ) a solvent for swelling the polyethylene from hydrogen , C - C . alkyl, C , -C6 haloalkyl , C1- C6 terephthalate ; hydroxyalkyl, optionally substituted C3 - C , cycloalkyl, [0030 ] ( b ) methanol; and optionally substituted (C7 - C . alkyl) ( C3 - C , cycloalkyl) , [ 0031 ] ( c ) a sub - stoichiometric amount of an alkoxide. optionally substituted aryl, and optionally substituted [0032 ] In some embodiments , the solvent for swelling the ( C . - C . alkyl )( aryl ) ; provided that one of R ' or R is not polyethylene terephthalate is selected from a halogenated hydrogen ; solvent, DMSO , benzyl alcohol, methanol, and any combi [0009 ] the process comprising admixing the polyester nations thereof. with a mixture comprising : [0033 ] In some embodiments , the ratio of polyethylene [0010 ] ( a ) a solvent for swelling the polyester ; terephthalate to alkoxide is between about 20 : 1 and about [ 0011 ] ( b ) an alcoholic solvent ; and 25 : 1 ( w : w ) . US 2019 / 0256450 A1 Aug . 22 , 2019 [0034 ] In some embodiments , the alkoxide is selected pared by alternating oxidation and methyl- esterification from sodium methoxide, potassium ethoxide, aluminium steps from para -xylene via methyl para - toluate . The method tri - n - propoxide , and tetrabutylammonium methoxide . for the production of DMT from para - xylene and methanol [ 0035 ]. In some embodiments , the ratio of solvent for consists of four major steps: oxidation , esterification , distil swelling the polyester to methanol is between about 0 . 5 : 1 lation , and crystallization . A mixture of para -xylene and and about 1 : 1 ( w : W ) . pare - toluic ester is oxidized with air in the presence of a [0036 ] In some embodiments , the admixing of the poly transition metal catalyst ( Co/ Mn ). The acid mixture result ethylene terephthalate with the solvent for swelling the ing from the oxidation is esterified with methanol to produce polyethylene terephthalate , the alkoxide , and the methanol is a mixture of esters . The crude ester mixture is distilled to performed until an about 80 % yield of dimethyl terephtha remove all the heavy boilers and residue produced ; the late is achieved . lighter esters are recycled to the oxidation section . The raw [ 0037 ]. Also disclosed herein is a reaction mixture com DMT is then crystallized to remove DMT isomers, residual prising : acids , and aromatic aldehydes . [0038 ] (a ) a polyester selected from polyethylene [0051 ] An Improvement in DMT production from PET terephthalate and poly ( ethylene glycol - co - 1 , 4 - cyclo recycling : due to the growing use of PET and PETG in the hexanedimethanol terephthalate ) ; packaging and fiber ( carpet and other textile ) industries there [0039 ] ( b ) a solvent for swelling the polyester; is a need for an efficient, low energy, high yielding , and cost 10040 ] ( c ) an alcoholic solvent; and effective way to form DMT from PET or PETG . [0041 ] ( d ) a sub - stoichiometric amount of an alkoxide . [0042 ] In some embodiments , the alcoholic solvent is Polyesters selected from methanol, ethanol, n - propanol, isopropanol, [ 0052 ] Described herein is a process for the transformation t - butanol, ethylene glycol , glycerol , cyclohexane - 1 , 4 - di of a polyester into an ester derivative ; the process compris yldimethanol,
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