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 ) 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 ) ( - co - 1 , 4 - 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 , ethanol, n -propanol , isopropanol, t -butanol , ethylene glycol, glycerol, - 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 is selected from a non polar solvent, a polar aprotic derivatives from 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 (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 - 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, phenol, benzyl alcohol, and any combinations ing admixing the polyester with a mixture comprising : thereof. [0053 ] ( a ) a solvent for swelling the polyester ; 100431 In some embodiments , the solvent for swelling the [0054 ] ( b ) an alcoholic solvent; and polyester is selected from a non polar solvent, a polar aprotic [0055 ] ( c ) a sub -stoichiometric amount of an alkoxide . solvent, a polar protic solvent, and any combinations [0056 ] In some embodiments , the polyester is selected thereof. from polyethylene terephthalate (PET ), poly ( ethylene gly [0044 ] In some embodiments , the solvent for swelling the col- co - 1, 4 -cyclohexanedimethanol terephthalate ) (PETG ), polyester is a halogenated solvent and the alcoholic solvent polyglycolide or polyglycolic acid (PGA ) , polylactic acid is methanol. (PLA ) , polycaprolactone ( PCL ) , polyhydroxybutyrate 10045 ] In some embodiments , the ratio of solvent for ( PHB ) , polyethylene adipate (PEA ), polybutylene succinate swelling the polyester to alcoholic solvent is between about (PBS ) , poly ( 3 -hydroxybutyrate - co - 3 -hydroxyvalerate ) 0 . 5 : 1 and about 1 : 1 ( w : W ) . (PHBV ) , polybutylene terephthalate (PBT ) , polytrimethyl 10046 ] In some embodiments , the ratio of polyester to ene terephthalate (PTT ), polyethylene naphthalate (PEN ) , alkoxide is between about 15 : 1 and about 30 : 1 ( w : w ) . Vectran® , cutin , and any combinations thereof. [0047 ] In some embodiments, the alkoxide is selected [ 0057 ] In some embodiments , the polyester is polyethyl from sodium methoxide , potassium ethoxide , aluminium ene terephthalate (PET ) : tri- n -propoxide , and tetrabutylammonium methoxide . [0048 ] In some embodiments , the alkoxide is sodium methoxide . DETAILED DESCRIPTION OF THE INVENTION [ 0049 ] Dimethyl terephthalate (DMT ) is used in the pro duction of polyesters , including polyethylene terephthalate ( PET ) , polytrimethylene terephthalate (PTT ) , and polybu tylene terephthalate (PBT ) . Because DMT is volatile , it is an intermediate in some schemes for the recycling of PET, e . g . from plastic bottles. Hydrogenation of DMT affords the diol 1 , 4 - cyclohexanedimethanol, which is a useful monomer in [ 0058 ] In some embodiments , the polyester is a the formation of polyester resins . terephthalic acid / ethylene glycol oligomer . [0050 ] DMT has been produced in a number of ways. [ 0059 ] In some embodiments , the polyester is poly ( ethyl Conventionally and still of commercial value is the direct ene glycol- co - 1, 4 -cyclohexanedimethanol terephthalate ) esterification of terephthalic acid . Alternatively , it is pre - (PETG ) :

HO tiqlobalaust ?? . US 2019 / 0256450 A1 Aug . 22 , 2019

[ 0060 ] In some embodiments , the polyester is polygly [0066 ] In some embodiments , the polyester is poly ( 3 colide or polyglycolic acid (PGA ), hydroxybutyrate -co - 3 -hydroxyvalerate ) (PHBV ):

HI ??

[0061 ] In some embodiments , the polyester is polylactic [0067 ] In some embodiments , the polyester is polybuty acid ( PLA ) : lene terephthalate (PBT ) : tri pe [ 0062 ] In some embodiments , the polyester is polycapro lactone (PCL ) : [0068 ] In some embodiments , the polyester is polytrim ethylene terephthalate (PTT ):

[0063 ] In some embodiments , the polyester is polyhy droxybutyrate (PHB ) :

CH3 il [0069 ] In some embodiments , the polyester is polyethyl to , OH ene naphthalate (PEN ) : [0064 ] In some embodiments , the polyester is polyethyl ene adipate ( PEA ) : fronto OH [0070 ] In some embodiments , the polyester is Vectran : [ 0065 ] In some embodiments , the polyester is polybuty somlene succinate (PBS )man : to read to fol1001to [0071 ] In some embodiments , the polyester is cutin . Cutin is one of two waxy polymers that are the main components of the plant cuticle , which covers all aerial surfaces of plants . Cutin consists of omega hydroxy acids and their derivatives , which are interlinked via ester bonds, forming a polyester frent polymer . There are two major monomer families of cutin , the C16 and C18 families. The C16 family consists mainly US 2019 / 0256450 A1 Aug . 22 , 2019 of 16 -hydroxy palmitic acid and 9 , 16 - or 10 , 16 -dihydroxy and the ester derivative is a terephthalate derivative . In some palmitic acid . The C18 family consists mainly of 18 -hy embodiments , the terephthalate derivative is a compound of droxy oleic acid , 9 , 10 - epoxy - 18 -hydroxy stearic acid , and formula (I ) : 9 , 10 , 18 - trihydroxystearate . Tomato cutin consists of 16 -hy droxy palmitic acid and 10 , 16 -dihydroxypalmitic acid where the 10 - isomer is largely dominant. The tomato cutin is a polyester biopolymer interesterificated . The significant pro Formula ( I ) portion of secondary esters ( esterification in the C - 10 sec ondary hydroxyl) shows that the polyester structure is sig nificantly branched . R1 - 0 O - R2; Ester Derivatives [0072 ] Described herein is a process for the transformation [ 0087 ] wherein R and R2 are independently selected from of a polyester into an ester derivative ; the process compris hydrogen , C . - C . alkyl, C1- C6 haloalkyk C -Co hydroxy ing admixing the polyester with a mixture comprising: alkyl, optionally substituted Cz -Cg cycloalkyl, optionally [0073 ] ( a ) a solvent for swelling the polyester ; substituted (C -C6 alkyl )( C3 - C , cycloalkyl) , optionally [ 0074 ] (b ) an alcoholic solvent; and substituted aryl, and optionally substituted (C1 - C6 alkyl) 10075 ] ( c ) a sub - stoichiometric amount of an alkoxide . (aryl ) ; provided that one of R ' or R is not hydrogen . 100761 In some embodiments , the polyester is polygly [ 0088 ] In some embodiments of a compound of Formula colide or polyglycolic acid (PGA ) and the ester derivative is (I ), R1 and R² are independently CZ -C6 alkyl or CZ -C6 a 2 -hydroxyacetate derivative . In some embodiments, the hydroxyalkyl. ester derivative is methyl 2 -hydroxyacetate . [ 0077 ] In some embodiments , the polyester is polylactic [0089 ] In some embodiments of a compound of Formula acid ( PLA ) and the ester derivative is a 2 -hydroxypropano ( I ), R and R are independently C . - C6 alkyl . In some ate derivative . In some embodiments , the ester derivative is embodiments of a compound of Formula (I ) , R and R2 are methyl 2 -hydroxypropanoate . independently methyl, ethyl, propyl, isopropyl, or butyl. In [0078 ] In some embodiments , the polyester is polycapro some embodiments of a compound of Formula ( I) , R . and R ? lactone (PCL ) and the ester derivative is a 6 -hydroxy are independently methyl or ethyl. In some embodiments of hexanoate derivative . In some embodiments , the ester a compound of Formula (I ) , R and R2 are methyl. In some derivative is a methyl 6 -hydroxyhexanoate . embodiments of a compound of Formula ( I ) , R1 and R2 are [ 0079 ] In some embodiments , the polyester is polyhy ethyl. In some embodiments of a compound of Formula ( I ) , droxybutyrate ( PHB ) and the ester derivative is a hydroxy R and R2 are not hydrogen . butyrate derivative . In some embodiments , the ester deriva [0090 ] In some embodiments of a compound of Formula tive is methyl hydroxybutyrate . ( I ) , R and R² are independently C7 -C6 hydroxyalkyl. In [0080 ] In some embodiments , the polyester is polyethyl some embodiments of a compound of Formula ( I ) , R1 and R ? ene adipate ( PEA ) and the ester derivative is an adipate are independently hydroxyethyl or propanediol. In some derivative . In some embodiments , the ester derivative is embodiments of a compound of Formula ( I) , R1 and R2 are dimethyl adipate . hydroxyethyl. In some embodiments of a compound of [0081 ] In some embodiments , the polyester is polybuty Formula ( I ) , R1 and R2 are 2 - hydroxyethyl. In some embodi lene succinate ( PBS ) and the ester derivative is a succinate ments of a compound of Formula ( I ) , R and R2 are dihy derivative . In some embodiments , the ester derivative is droxypropyl. In some embodiments of a compound of dimethyl succinate . Formula (I ) , R and R ? are 2 ,3 -dihydroxypropyl . [0082 ] In some embodiments , the polyester is poly ( 3 [0091 ] In some embodiments of a compound of Formula hydroxybutyrate - co - 3 -hydroxyvalerate ) ( PHBV ) and the (I ), R and R are independently optionally substituted ester derivative is a hydroxybutyrate derivative , a hydroxy ( C . - C . alkyl) ( C3 - C , cycloalkyl) . In some embodiments of a valerate derivative , or a combination thereof. In some compound of Formula ( I) , R and R ’ are independently embodiments , the ester derivative is methyl hydroxybu substituted (C , -Co alkyl) (CZ - C , cycloalkyl) . In some tyrate , methyl hydroxyvalerate , or a combination thereof. embodiments of a compound of Formula ( I ) , R and R2 are [ 0083 ] In some embodiments, the polyester is polyethyl 4 - hydroxymethyl) cyclohexyl) methyl . ene naphthalate (PEN ) and the ester derivative is a naph [0092 ] In some embodiments of a compound of Formula thalate derivative . In some embodiments , the ester derivative (I ) , R . and R2 are independently optionally substituted aryl. is dimethyl naphthalate . In some embodiments of a compound of Formula ( I) , R ' and [0084 ] In some embodiments, the polyester is vectran and R ? are phenyl . the ester derivative is a naphthoate derivative , a benzoate [0093 ] In some embodiments of a compound of Formula derivative, or a combination thereof. In some embodiments , (1 ) , R1 and R2 are independently optionally substituted the ester derivative is methyl hydroxynaphthoate or methyl ( C , - C alkyl) ( aryl) . In some embodiments of a compound of hydroxybenzoate . Formula (I ), R and R2 are benzyl. [ 0085 ] In some embodiments , the polyester is cutin and [0094 ] In some embodiments , the ester derivative contains the ester derivative is a hydroxypalmitate or a dihydroxyp less than about 10 % impurity ( w / w ) . In some embodiments , almitate derivative . In some embodiments , the ester deriva the ester derivative contains less than about 9 % impurity tive is methyl hydroxypalmitate or methyl dihydroxypalmi ( w / w ) . In some embodiments , the ester derivative contains tate . less than about 8 % impurity ( w / w ) . In some embodiments , [0086 ] In some embodiments , the polyester is polyethyl the ester derivative contains less than about 7 % impurity ene terephthalate (PET ), poly ( ethylene glycol- co - 1, 4 -cyclo ( w / w ) . In some embodiments , the ester derivative contains hexanedimethanol terephthalate ) ( PETG ) , polytrimethylene less than about 6 % impurity ( w / w ) . In some embodiments , terephthalate (PTT ) , or polybutylene terephthalate (PBT ) the ester derivative contains less than about 5 % impurity US 2019 / 0256450 A1 Aug . 22 , 2019

( w / w ) . In some embodiments , the ester derivative contains (0101 ] In some embodiments , the alcoholic solvent is a less than about 4 % impurity ( w / w ) . In some embodiments, linear C , - C4 alcohol . In some embodiments, the alcoholic the ester derivative contains less than about 3 % impurity solvent is methanol, ethanol, propanol, butanol, or a com ( w / w ) . In some embodiments , the ester derivative contains bination thereof . In some embodiments , the alcoholic sol less than about 2 % impurity ( w / w ) . In some embodiments , vent is methanol, ethanol, propanol, or a combination the ester derivative contains less than about 1 % impurity thereof. In some embodiments , the alcoholic solvent is ( w / w ) . In some embodiments , the ester derivative contains methanol. In some embodiments , the alcohol is ethanol. In less than about 0 . 5 % impurity ( w / w ) . In some embodiments , some embodiments , the alcoholic solvent is a branched the ester derivative contains less than about 0 . 4 % impurity C3- C4 alcohol. In some embodiments , the alcoholic solvent ( w / w ) . In some embodiments , the ester derivative contains is t - butanol , s - butanol , i -butanol , propanol, or any combi less than about 0 . 3 % impurity ( w / w ) . In some embodiments , nations thereof. In some embodiments , the alcoholic solvent the ester derivative contains less than about 0 .2 % impurity is a cyclic C3 - C , alcohol. In some embodiments, the alco ( w / w ) . In some embodiments, the ester derivative contains holic solvent is cyclopropanol, cyclobutanol, cyclopentanol, less than about 0 . 1 % impurity ( w / w ). cyclohexanol, cycloheptanol, cyclohexane- 1 , 4 - diyldimetha [0095 ] In some embodiments , the ester derivative contains nol , or any combinations thereof . In some embodiments , the less than about 250 ppm of any metals , less than about 240 alcoholic solvent is cyclohexane - 1 ,4 - diyldimethanol. ppm of any metals, less than about 230 ppm of any metals , [0102 ] In some embodiments , the alcoholic solvent is a less than about 220 ppm of any metals , less than about 210 polyol. In some embodiments , the alcoholic solvent is ppm of any metals , less than about 200 ppm of any metals , selected from ethylene glycol, glycerol, and any combina less than about 190 ppm of any metals , less than about 180 tions thereof. ppm of any metals , less than about 170 ppm of any metals , [0103 ] In some embodiments , the alcoholic solvent is less than about 160 ppm of any metals , less than about 150 selected from phenol, benzyl alcohol, and any combinations ppm of any metals , less than about 140 ppm of any metals , thereof. less than about 130 ppm of any metals, less than about 120 ppm of any metals , less than about 110 ppm of any metals , Solvent for Swelling the Polyester less than about 100 ppm of any metals , less than about 90 [0104 ] Described herein is a process for the transformation ppm of any metals , less than about 80 ppm of any metals , of a polyester into an ester derivative ; the process compris less than about 70 ppm of any metals , less than about 60 ppm ing admixing the polyester with a mixture comprising : of any metals , less than about 50 ppm of any metals , less [0105 ] (a ) a solvent for swelling the polyester; than about 40 ppm of any metals , less than about 30 ppm of [ 0106 ] (b ) an alcoholic solvent; and any metals , less than about 20 ppm of any metals , less than [0107 ] (c ) a sub -stoichiometric amount of an alkoxide. about 10 ppm of any metals , less than about 5 ppm of any [0108 ] In some embodiments , the process described herein metals , less than about 4 ppm of any metals , less than about comprises pre- treating the polyester with a solvent for 3 ppm of any metals , less than about 2 ppm of any metals , swelling the polyester prior to the addition of the alcoholic less than about 1 ppm of any metals , less than about 0 . 9 ppm solvent and alkoxide . In some embodiments , the pre - treat of any metals , less than about 0 . 8 ppm of any metals , less ment with the solvent for swelling the polyester is done for than about 0 . 7 ppm of any metals , less than about 0 . 6 ppm between about 5 mins and about 60 mins prior to the of any metals , less than about 0 . 5 ppm of any metals , less addition of the alcoholic solvent and alkoxide . In some than about 0 . 4 ppm of any metals , less than about 0 . 3 ppm embodiments , the pre - treatment with the solvent for swell of any metals , less than about 0 . 2 ppm of any metals , less ing the polyester is done for between about 5 mins and about than about 0 . 1 ppm of any metals , less than about 0 . 09 ppm 40 mins prior to the addition of the alcoholic solvent and of any metals , less than about 0 .08 ppm of any metals , less alkoxide . In some embodiments , the pre - treatment with the than about 0 .07 ppm of any metals , less than about 0 .06 ppm solvent for swelling the polyester is done for between about of any metals , less than about 0 . 05 ppm of any metals , less 5 mins and about 20 mins prior to the addition of the than about 0 .04 ppm of any metals , less than about 0 .03 ppm alcoholic solvent and alkoxide . In some embodiments , the of any metals , less than about 0 .02 ppm of any metals , or less pre -treatment with the solvent for swelling the polyester is than about 0 . 01 ppm of any metals . done for between about 5 mins and about 10 mins prior to the addition of the alcoholic solvent and alkoxide. In some Alcoholic Solvent embodiments , the pre - treatment with the solvent for swell [ 0096 ] Described herein is a process for the transformation ing the polyester is done for about 5 mins . In some embodi of a polyester into an ester derivative ; the process compris ments , the pre -treatment with the solvent for swelling the ing admixing the polyester with a mixture comprising : polyester is done for about 10 mins . In some embodiments , the pre - treatment with the solvent for swelling the polyester [0097 ] ( a ) a solvent for swelling the polyester ; is done for about 15 mins . In some embodiments , the [ 0098 ] ( b ) an alcoholic solvent ; and pre - treatment with the solvent for swelling the polyester is [0099 ] (c ) a sub - stoichiometric amount of an alkoxide . done for about 20 mins. In some embodiments , the pre 10100 ] In some embodiments , the process described herein treatment with the solvent for swelling the polyester is done comprises an alcoholic solvent. In some embodiments , the for about 25 mins . In some embodiments , the pre - treatment alcoholic solvent is a linear alcohol, branched alcohol, cyclic with the solvent for swelling the polyester is done for about alcohol, or any combinations thereof. In some embodiments , 30 mins . In some embodiments , the pre - treatment with the the alcoholic solvent is selected from methanol, ethanol, solvent for swelling the polyester is done for about 35 mins. n -propanol , isopropanol, t - butanol, ethylene glycol, glyc In some embodiments , the pre - treatment with the solvent for erol, cyclohexane - 1 , 4 - diyldimethanol, phenol, benzyl alco swelling the polyester is done for about 40 mins . In some hol, and any combinations thereof. embodiments , the pre - treatment with the solvent for swell US 2019 / 0256450 A1 Aug . 22 , 2019 ing the polyester is done for about 45 mins . In some [0114 ] ( a ) a solvent for swelling the polyester ; embodiments , the pre- treatment with the solvent for swell [ 0115 ] ( b ) an alcoholic solvent; and ing the polyester is done for about 50 mins. In some [0116 ] ( c ) a sub - stoichiometric amount of an alkoxide . embodiments , the pre - treatment with the solvent for swell [0117 ] In some embodiments , the process described herein ing the polyester is done for about 55 mins. In some comprises adding a sub -stoichiometric amount of an alkox embodiments , the pre - treatment with the solvent for swell ide . In some embodiments , the process described herein ing the polyester is done for about 60 mins. comprises adding a catalytic amount of an alkoxide. 10109 ] In some embodiments, the process described herein [0118 ] “ Sub - stoichiometric amount” , as used herein , is comprises treating the polyester with a solvent for swelling used to indicate that the amount of material used is less than the polyester at the same time as the addition of the alcoholic a stoichiometric amount. The term is used herein inter solvent and alkoxide . changeably with “ catalytic amount. ” In some embodiments , [ 0110 ] In some embodiments , the solvent for swelling the a sub - stoichiometric amount is less than or equal to about polyester is selected from a non polar solvent, a polar aprotic 95 % of a stoichiometric amount . In some embodiments , a solvent, a polar protic solvent, and any combinations sub -stoichiometric amount is less than or equal to about 90 % thereof. of a stoichiometric amount. In some embodiments , a sub [0111 ] In some embodiments , the solvent for swelling the stoichiometric amount is less than or equal to about 85 % of polyester is selected from dimethyl sulfoxide (DMSO ), a stoichiometric amount. In some embodiments , a sub N , N - dimethylformamide (DMF ) , acetone , a halogenated stoichiometric amount is less than or equal to about 80 % of solvent, n -hexane , nitrobenzene , methanol, benzyl alcohol, a stoichiometric amount. In some embodiments , a sub benzaldehyde , and any combinations thereof. In some stoichiometric amount is less than or equal to about 75 % of embodiments , the solvent for swelling the polyester is a stoichiometric amount. In some embodiments , a sub selected from DMSO , a halogenated solvent, and any com stoichiometric amount is less than or equal to about 70 % of binations thereof. In some embodiments , the solvent for a stoichiometric amount. In some embodiments , a sub swelling the polyester is DMSO . In some embodiments , the stoichiometric amount is less than or equal to about 65 % of solvent for swelling the polyester is a halogenated solvent . a stoichiometric amount. In some embodiments , a sub In some embodiments, the solvent for swelling the polyester stoichiometric amount is less than or equal to about 60 % of is a chlorinated solvent. In some embodiments , the solvent a stoichiometric amount . In some embodiments , a sub for swelling the polyester is dichloromethane , dichloroeth stoichiometric amount is less than or equal to about 55 % of ane, tetrachloroethane , chloroform , tetrachloromethane , a stoichiometric amount. In some embodiments , a sub trichloroethane , or any combinations thereof. In some stoichiometric amount is less than or equal to about 50 % of embodiments , the solvent for swelling the polyester is a stoichiometric amount. In some embodiments , a sub dichloromethane . In some embodiments , the solvent for stoichiometric amount is less than or equal to about 45 % of swelling the polyester is methanol. a stoichiometric amount. In some embodiments , a sub 0112 ] In some embodiments , the ratio of solvent for stoichiometric amount is less than or equal to about 40 % of swelling the polyester to alcoholic solvent is between about a stoichiometric amount. In some embodiments , a sub 0 . 1 : 1 and about 2 : 1 ( w :W ). In some embodiments, the ratio stoichiometric amount is less than or equal to about 35 % of of solvent for swelling the polyester to alcoholic solvent is a stoichiometric amount. In some embodiments , a sub between about 1 : 1 and about 2 : 1 (w :W ) . In some embodi stoichiometric amount is less than or equal to about 30 % of ments , the ratio of solvent for swelling the polyester to a stoichiometric amount. In some embodiments , a sub alcoholic solvent is between about 0 . 1 : 1 and about 2 : 1 stoichiometric amount is less than or equal to about 25 % of ( w : W ) , or between about 0 . 2 : 1 and about 2 : 1 ( w : W ) , or a stoichiometric amount. In some embodiments, a sub between about 0 . 3 : 1 and about 2 : 1 ( w : W ), or between about stoichiometric amount is less than or equal to about 20 % of 0 . 4 : 1 and about 2 : 1 ( w : W ) , or between about 0 . 5 : 1 and about a stoichiometric amount. In some embodiments , a sub 2 : 1 (w : W ), or between about 0 .6 : 1 and about 2 : 1 (w :W ), or stoichiometric amount is less than or equal to about 15 % of between about 0 . 7 : 1 and about 2 : 1 ( w : W ) , or between about a stoichiometric amount. In some embodiments , a sub 0 . 8 : 1 and about 2 : 1 ( w : W ) , or between about 0 . 9 : 1 and about stoichiometric amount is less than or equal to about 10 % of 2 : 1 ( w : W ) , or between about 1 : 1 and about 2 : 1 ( w : W ) , or a stoichiometric amount . between about 1 : 2 and about 2 : 1 ( w : W ) , or between about [0119 ] " Stoichiometric amount” , as used herein , is used to 1 : 3 and about 2 : 1 ( w : W ) , or between about 1 : 4 and about 2 : 1 indicate that the amount ofmaterial used is equivalent to the ( w : W ) , or between about 1 : 4 and about 2 : 1 ( w : W ) , or number of ester linkages present in the polyester. between about 1 : 6 and about 2 : 1 ( w : W ) , or between about [0120 ] In some embodiments , the alkoxide , which com 1 :7 and about 2 : 1 (w :W ), or between about 1 : 8 and about 2 : 1 prises an alkoxide anion and a cation is selected from an ( w : W ) , or between about 1 : 9 and about 2 : 1 ( w : W ) , or alkali metal alkoxide, an alkaline earth metal alkoxide , a between about 0 . 5 : 1 and about 1 . 5 : 1 ( w : W ) , or between metal alkoxide , an ammonium alkoxide , and any combina about 0 . 8 : 1 and about 1 . 2 : 1 ( w : W ) , or between about 0 . 5 : 1 tions thereof. In some embodiments , the alkoxide anion is a and about 1 : 1 ( w : w ) , or between about 1 : 1 and about 1 . 5 : 1 C -C4 alkoxide anion . In some embodiments , the alkoxide ( w : W ) . In some embodiments , the ratio of solvent for swell anion is selected from methoxide , ethoxide , n - propoxide , ing the polyester to alcoholic solvent is between about 0 . 5 : 1 n - butoxide , t -butoxide , sec -butoxide , iso -butoxide , iso and about 1 : 1 (w : w ) . propoxide , and a combination thereof. In some embodi ments , the alkoxide anion is methoxide, ethoxide , or any Alkoxides combinations thereof . In some embodiments , the alkoxide [0113 ] Described herein is a process for the transformation anion is methoxide . In some embodiments , the cation is of a polyester into an ester derivative ; the process compris - lithium , sodium , potassium , magnesium , calcium , strontium , ing admixing the polyester with a mixture comprising: barium , zinc, aluminum , or ammonium . In some embodi US 2019 / 0256450 A1 Aug . 22 , 2019

ments , the alkoxide is sodium methoxide , potassium ethox - mins and 2 hrs , or between about 20 mins and 2 hrs , or ide, or aluminium tri - n - propoxide. In some embodiments , between about 30 mins and 2 hrs , or between about 40 mins the ammonium alkoxide is a tetraalkylammonium alkoxide . and 2 hrs , or between about 30 mins and 1 hr, or between In some embodiments , the ammonium alkoxide is a tetra about 30 mins and 1 . 5 hrs. In some embodiments , the butylammonium alkoxide . In some embodiments , the alkox admixing of the polyester with the solvent for swelling the ide is sodium methoxide , potassium ethoxide , aluminium polyester, the alkoxide, and the alcoholic solvent is per tri- n -propoxide , or tetrabutylammonium methoxide . formed for about 10 mins , or about 15 mins , or about 20 10121] In some embodiments , the alkoxide is generated mins , or about 25 mins , or about 30 mins , or about 35 mins , in - situ by addition of an alkalimetal , an alkaline earth metal, or about 40 mins , or about 45 mins, or about 50 mins, or or a metal to the alcoholic solvent. about 60 mins , or about 70 mins , or about 80 mins , or about [0122 ] In some embodiments , the ratio of polyester to 90 mins , or about 100 mins , or about 110 mins, or about 120 alkoxide is between about 15 : 1 and about 125 : 1 ( w : W ) , or mins, or about 130 mins, or about 140 mins , or about 150 between about 15 : 1 and about 100 :1 ( w : w ), or between mins , or about 160 mins , or about 170 min , or about 180 about 15 : 1 and about 80 : 1 ( w : W ) , or between about 15 : 1 and mins . In some embodiments , the admixing of the polyester about 60 : 1 ( W : W ) , or between about 15 : 1 and about 40 : 1 with the solvent for swelling the polyester , the alkoxide , and ( w : W ) , or between about 15 : 1 and about 25 : 1 ( w : W ) , or the alcoholic solvent is performed for about 1 hr, or about 2 between about 15 : 1 and about 20 : 1 ( w : W ) , or between about hrs , or about 3 hrs , about 4 hrs , or about 5 hrs . 20 : 1 and about 25 : 1 (w : W ) , or between about 20 : 1 and about 50 : 1 ( w : w ) , or between about 30 : 1 and about 60 : 1 ( w : w ) , or Temperature between about 40 : 1 and about 70 : 1 ( w : w ), or between about 50 : 1 and about 80 : 1 ( w : W ) , or between about 60 : 1 and about [0129 ] Described herein is a process for the transformation 90 : 1 ( w : W ) , or between about 20 : 1 and about 125 : 1 ( w : W ) , of a polyester into an ester derivative; the process compris or between about 40 : 1 and about 125 : 1 (w :W ), or between ing admixing the polyester with a mixture comprising : about 60 : 1 and about 125 : 1 ( w : W ), or between about 80 : 1 [ 0130 ] (a ) a solvent for swelling the polyester ; and about 125 : 1 ( w : W ) , or between about 100 : 1 and about [0131 ] ( b ) an alcoholic solvent; and 125 : 1 ( w : W ) . In some embodiments , the ratio of polyester to [0132 ] (c ) a sub - stoichiometric amount of an alkoxide . alkoxide is between about 20 : 1 and about 25 : 1 ( w : W ) . [0133 ] In some embodiments, the process disclosed herein is conducted at ambient temperature . In some embodiments , Reaction Time ambient temperature is 25 + 5° C . [0134 ] In some embodiments , the process disclosed herein [ 0123] Described herein is a process for the transformation is conducted without external heat. In some embodiments , of a polyester into an ester derivative ; the process compris the process is exothermic and the temperature of the reaction ing admixing the polyester with a mixture comprising : mixture rises to at least 30° C . , at least 35° C ., at least 40° [0124 ] (a ) a solvent for swelling the polyester ; C . , at least 45° C . , at least 50° C . , at least 55° C . , or at least [0125 ] ( b ) an alcoholic solvent; and 60° C . In some embodiments , no external heat sources are [0126 ] (c ) a sub - stoichiometric amount of an alkoxide . used to increase the temperature of the reaction mixture . [0127 ] In some embodiments , the admixing of the poly [0135 ] In some embodiments , the process disclosed herein ester with the solvent for swelling the polyester, the alkox is conducted with external heat . In some embodiments , the ide , and the alcoholic solvent is performed for a sufficient process disclosed herein is conducted with external heat at time. In some embodiments , the admixing of the polyester between about 25° C . and about 80° C . , or between about with the solvent for swelling the polyester, the alkoxide , and 25° C . and about 60° C ., or between about 40° C . and about the alcoholic solvent is performed until an about 70 % yield 60° C ., or between about 40° C . and about 50° C ., or of desired ester is achieved . In some embodiments , the between about 30° C . and about 50° C . In some embodi admixing of the polyester with the solvent for swelling the ments , the process disclosed herein is conducted at about 26° polyester, the alkoxide , and the alcoholic solvent is per C ., about 27° C . , about 28° C . , about 29° C ., about 30° C . , formed until an about 75 % yield of desired ester is achieved . about 31° C ., about 32° C . , about 33° C . , about 34° C ., about In some embodiments , the admixing of the polyester with 35° C . , about 36° C . , about 37° C ., about 38° C . , about 390 the solvent for swelling the polyester, the alkoxide , and the C ., about 40° C ., about 41° C . , about 42° C ., about 43° C ., alcoholic solvent is performed until an about 80 % yield of about 44° C . , about 45° C ., about 46° C . , about 47° C . , about desired ester is achieved . In some embodiments , the admix ing of the polyester with the solvent for swelling the 48° C . , about 49° C . , about 50° C ., about 51° C . , about 52° polyester, the alkoxide , and the alcoholic solvent is per C ., about 53° C ., about 54° C ., about 55° C ., about 56° C ., formed until an about 85 % yield of desired ester is achieved . about 57° C . , about 58° C ., about 59° C . , about 60° C ., about In some embodiments , the admixing of the polyester with 65° C ., about 70° C . , about 75° C ., or about 80° C . the solvent for swelling the polyester, the alkoxide , and the alcoholic solvent is performed until an about 90 % yield of Pressure desired ester is achieved . In some embodiments, the admix [0136 ] In some embodiments , the process disclosed herein ing of the polyester with the solvent for swelling the is conducted at atmospheric pressure . In some embodiments , polyester, the alkoxide , and the alcoholic solvent is per the process disclosed herein is conducted at elevated pres formed until an about 95 % yield of desired ester is achieved . sures . In some embodiments , the process disclosed herein is [ 0128 ] In some embodiments , the admixing of the poly conducted at a pressure between about atmospheric pressure ester with the solvent for swelling the polyester, the alkox and about 220 psi , or between about atmospheric pressure ide , and the alcoholic solvent is performed for between and about 200 psi , or between about atmospheric pressure about 10 mins and 5 hrs , or between about 10 mins and 4 hrs , and about 150 psi, or between about atmospheric pressure or between about 10 mins and 3 hrs , or between about 10 and about 100 psi , or between about atmospheric pressure US 2019 / 0256450 A1 Aug . 22 , 2019

and about 50 psi, or between about 20 and about 150 psi , or [0148 ] As used herein , ambient temperature is a colloquial between about 50 and about 100 psi. In some embodiments , expression for the typical or preferred indoor ( climate the process disclosed herein is conducted at about 14 psi , controlled ) temperature to which people are generally accus about 15 psi, about 16 psi, about 17 psi, about 18 psi, about tomed . It represents the small range of temperatures at which 19 psi, about 20 psi, about 30 psi , about 40 psi , about 50 psi , the air feels neither hot nor cold , approximately 21° C . In about 60 psi , about 70 psi, about 80 psi , about 90 psi, about some embodiments , ambient temperature is 25 + 5° C . In 100 psi , about 110 psi, about 120 psi , about 130 psi, about some embodiments , ambient temperature is 18° C . In some 140 psi , about 150 psi , about 160 psi, about 170 psi, about embodiments , ambient temperature is 19° C . In some 180 psi , about 190 psi , about 200 psi, about 210 psi , or about embodiments , ambient temperature is 20° C . In some 220 psi . embodiments , ambient temperature is 21° C . In some embodiments , ambient temperature is 22° C . In some Agitation embodiments , ambient temperature is 23° C . In some embodiments , ambient temperature is 24° C . In some [ 0137 ] Described herein is a process for the transformation embodiments , ambient temperature is C . In some of a polyester into an ester derivative ; the process compris embodiments , ambient temperature is 26° C . In some ing admixing the polyester with a mixture comprising: embodiments , ambient temperature is 27° C . In some [0138 ] (a ) a solvent for swelling the polyester ; embodiments , ambient temperature is 28° C . In some [0139 ] (b ) an alcoholic solvent; and embodiments , ambient temperature is 29° C . In some [0140 ] ( c ) a sub - stoichiometric amount of an alkoxide . embodiments , ambient temperature is 30° C . [ 0141 ] In some embodiments , the process disclosed herein 10149 ) As used in this specification and the appended is conducted without agitation . In some embodiments , the claims, depolymerization , refer to a way of breaking down process disclosed herein is conducted with increased agita - a polymer to its starting material . It is essentially the tion . In some embodiments , a stirred batch reactor is used to opposite of polymerization . In some embodiments , the depo provide agitation . In some embodiments , a continuous reac lymerization is achieved by glycolysis , methanolysis or tor is used to provide agitation . hydrolysis , categorized by the depolymerization reactant used , such as glycol, methanol or water , respectively . Certain Terminology [0150 ] Definition of standard chemistry terms may be found in reference works , including but not limited to , Carey [0142 ] The section headings used herein are for organiza and Sundberg “ Advanced Organic Chemistry 4th Ed . ” Vols . tional purposes only and are not to be construed as limiting A (2000 ) and B (2001 ), Plenum Press , New York . the subject matter described . [0151 ] The terms below , as used herein , have the follow [ 0143 ] Unless defined otherwise , all technical and scien ing meanings, unless indicated otherwise : tific terms used herein have the same meaning as is com [0152 ] “ Alkyl” refers to a straight or branched hydrocar monly understood to which the claimed subject matter bon chain radical which is attached to the rest of the belongs. In the event that there are a plurality of definitions molecule by a single bond . A linear alkyl comprising up to for terms herein , those in this section prevail . 4 carbon atoms is referred to as a linear CZ -C4 alkyl , [0144 ] It is to be understood that the general description likewise , for example , a linear alkyl comprising up to 3 and the detailed description are exemplary and explanatory carbon atoms is a linear C , - Cz alkyl . Linear alkyl groups only and are not restrictive of any subject matter claimed . In include linear C - C4 alkyl, linear C , -Cz alkyl, linear C1- C2 this application , the use of the singular includes the plural alkyl, linear C2 -Cz alkyl and linear C2- C4 alkyl. Represen unless specifically stated otherwise . It must be noted that, as tative alkyl groups include , methyl, ethyl, propyl, and butyl. used in the specification and the appended claims, the A branched alkyl comprising between 3 and 4 carbon atoms singular forms “ a , " " an ” and “ the” include plural referents is referred to as a branched C3 -C4 alkyl. Representative unless the context clearly dictates otherwise . In this appli branched alkyl groups include , but are not limited to t -butyl , cation , the use of " or” means " and / or ” unless stated other sec -butyl , isobutyl, and isopropyl. Unless stated otherwise wise . Furthermore , use of the term “ including” as well as specifically in the specification , an alkyl is optionally sub other forms , such as " include ” , “ includes ," and " included ," stituted with oxo , halogen , CN , CF3, OH , — OMe, is not limiting . - NH2, or — NO2. In some embodiments, an alkyl is option [ 0145 ] Unless the context requires otherwise , throughout ally substituted with oxo , halogen , — CN , – CF3, OH , or the specification and claims which follow , the word " com OMe. In some embodiments , the alkyl is optionally prise ” and variations thereof, such as, “ comprises ” and substituted with halogen . " comprising” are to be construed in an open , inclusive sense , [0153 ] “ Halo ” or “ halogen ” refers to bromo, chloro , fluoro that is , as “ including , but not limited to . ” Further, headings or iodo . In some embodiments , halogen is fluoro or chloro . provided herein are for convenience only and do not inter In some embodiments , halogen is fluoro . pret the scope or meaning of the claimed invention . [0154 ] “ Haloalkyl” refers to an alkyl radical, as defined [0146 ] As used in this specification and the appended above , that is substituted by one or more halo atoms, as claims, the singular forms“ a , " " an ,” and “ the ” include plural defined above , e . g . , trifluoromethyl, difluoromethyl, fluo referents unless the content clearly dictates otherwise . It romethyl, trichloromethyl, 2 ,2 , 2 - trifluoroethyl, 1, 2 -difluoro should also be noted that the term “ or” is generally ethyl, 3 - bromo- 2 - fluoropropyl, 1 , 2 - dibromoethyl, and the employed in its sense including " and /or ” unless the content like . clearly dictates otherwise . [0155 ] “ Hydroxyalkyl” refers to an alkyl radical, as [0147 ] As used herein , the term “ about” or “ approxi defined above, that is substituted by one or more OH mately ” means within 10 % , preferably within 10 % , and groups, e .g . , hydroxymethyl, hydroxyethyl, hydroxypropyl, more preferably within 5 % of a given value or range . propanediol, and the like . US 2019 / 0256450 A1 Aug . 22 , 2019

[0156 ] " Cycloalkyl” refers to a stable , partially or fully spheric pressure for about 40 mins . Sodium methoxide and saturated , monocyclic or polycyclic carbocyclic ring , which methanol were then added to the reaction mixture was may include fused or bridged ring systems. Representative stirred and heated for 120 mins ( see table below for cycloalkyls include , but are not limited to , cycloalkyls amounts , time, and temperature details ) . having from three to fifteen carbon atoms (Cz -C15 [0160 ] The reaction mixture was then filtered and the filter cycloalkyl) , from three to ten carbon atoms (Cz - C1 cake was washed with methanol. The filter cake was then cycloalkyl) , from three to eight carbon atoms (C3 -C , melted and filtered at 140° C . to remove any unreacted cycloalkyl) , from three to six carbon atoms (C3 -Co materials . The filtered dimethyl terephthalate was then dis cycloalkyl) , from three to five carbon atoms (Cz - Ca tilled under vacuum at 200° C . The liquid recovered from cycloalkyl) , or three to four carbon atoms (C3 - C4 the filtration was distilled to recover the solvents and the cycloalkyl) . In some embodiments , the cycloalkyl is a 3 - to mono ethylene glycol. 6 -membered cycloalkyl. In some embodiments , the cycloalkyl is a 5 . to 6 -membered cycloalkyl. Monocyclic cycloalkyls include, for example , cyclopropyl, cyclobutyl, Weight of cyclopentyl , cyclohexyl, cycloheptyl, and cyclooctyl. Poly Weight of sodium Reaction Reaction cyclic cycloalkyls or carbocycles include , for example , methanol methoxide time temperature Yield adamantyl, norbornyl, decalinyl, bicyclo [ 3 . 3 . 0 ] octane, bicy (g ) (min ) (°C . ) ( % ) clo 4 . 3 . 0 ] nonane, cis - decalin , trans - decalin , bicyclo [ 2 . 1 . 1 ] Example 1A 667 32 120 JS 90 hexane , bicyclo [ 2 .2 .1 ]heptane , bicyclo [2 .2 . 2 ] octane , bicy Example 1B 600 54 120 50 90 clo [ 3 . 2 . 2 ]nonane , and bicyclo [ 3 . 3 . 2 ]decane , and 7 , 7 Example 10 580 50 120 60 90 dimethyl- bicyclo [ 2 . 2 . 1 ]heptanyl . Partially saturated cycloalkyls include , for example cyclopentenyl, cyclohex enyl, cycloheptenyl , and cyclooctenyl. Unless stated other Example 2 wise specifically in the specification , a cycloalkyl is option ally substituted with oxo , halogen , methyl , ethyl, CN , [0161 ] Polyethylene terephthalate ( 1000 g ) was intro - CF3, OH , — OMe, - NH2, or — NO2. In some embodi duced in a reactor. DMSO (500 g ) was added and the ments , a cycloalkyl is optionally substituted with oxo , mixture was stirred at room temperature and at atmospheric halogen , methyl , ethyl, CN , CF3, OH , or — OMe. In pressure for about 40 mins. Sodium methoxide (45 g ) and some embodiments , the cycloalkyl is optionally substituted methanol (550 g ) were then added to the reaction mixture with halogen . was stirred and heated at 55° C . for 120 mins . [0157 ] “ Aryl ” refers to a radical derived from a hydrocar [0162 ] The reaction mixture was then filtered and the filter bon ring system comprising hydrogen , 6 to 30 carbon atoms cake was washed with methanol. The filter cake was then and at least one aromatic ring . The aryl radical may be a melted and filtered at 140° C . to remove any unreacted monocyclic , bicyclic , tricyclic or tetracyclic ring system , materials . The filtered dimethyl terephthalate was then dis which may include fused or bridged ring systems. In some tilled under vacuum at 200° C . The liquid recovered from embodiments, the aryl is a 6 - to 10 -membered aryl. In some the filtration was distilled to recover the solvents and the embodiments , the aryl is a 6 -membered aryl. Aryl radicals mono ethylene glycol. include, but are not limited to , aryl radicals derived from the [0163 ] Dimethyl terephthalate was obtained in 89 % yield . hydrocarbon ring systems of anthrylene , naphthylene , 1 . - 30 . ( canceled ) phenanthrylene, anthracene, azulene, , chrysene, 31. A process for the transformation of a polyester fluoranthene, fluorene , as- indacene , s - indacene, indane , selected from polyethylene terephthalate and poly (ethylene indene , naphthalene , phenalene, phenanthrene , pleiadene , glycol- co - 1 , 4 - cyclohexanedimethanol terephthalate ) into pyrene , and triphenylene . In some embodiments , the aryl is dimethyl terephthalate ; phenyl. Unless stated otherwise specifically in the specifi the process comprising admixing the polyester with a cation , an aryl may be optionally substituted , for example , mixture comprising : with halogen , amino , nitrile , nitro , hydroxyl , alkyl, alkenyl, alkynyl, haloalkyl, alkoxy , aryl, cycloalkyl, heterocy ( a ) methanol; cloalkyl, heteroaryl , and the like . In some embodiments , an (b ) a sub - stoichiometric amount of an alkoxide; aryl is optionally substituted with halogen , methyl, ethyl, wherein the process is performed at a temperature CN , CF3, OH , OMe, - NH2, or — NO2. In some between about 25° C . and about 80° C .; embodiments , an aryl is optionally substituted with halogen , wherein the ratio of the polyester to the alkoxide is methyl, ethyl, CN , CF3, OH , or — OMe. In some between about 20 : 1 and about 50 : 1 ( w : W ); embodiments , the aryl is optionally substituted with halo and wherein the process achieves at least about 70 % yield gen . of dimethyl terephthalate . 32 . The process of claim 1 , wherein the alkoxide is EXAMPLES selected from an alkali metal alkoxide , an alkaline earth metal alkoxide , a metal alkoxide , an ammonium alkoxide [0158 ] The following examples are intended to illustrate and any combinations thereof. but not limit the disclosed embodiments . 33 . The process of claim 1 , wherein the alkoxide is selected from sodium methoxide, potassium ethoxide, alu Example 1 minium tri - n - propoxide , and tetrabutylammonium methox [0159 ] Polyethylene terephthalate ( 1000 g ) was intro ide. duced in a reactor. Dichloromethane (500 g ) was added and 34 . The process of claim 1 , wherein the alkoxide is the mixture was stirred at room temperature and at atmo sodium methoxide . US 2019 / 0256450 A1 Aug . 22 , 2019

35 . The process of claim 1 , wherein the alkoxide is generated in -situ by addition of an alkali metal, an alkaline earth metal, or a metal to the methanol. 36 . The process of claim 1 , wherein the ratio of the polyester to the alkoxide is between about 20 : 1 and about 25 : 1 ( w :w ). 37 . The process of claim 1 , wherein the process achieves at least about 80 % yield of dimethyl terephthalate . 38 . The process of claim 1 , wherein the process achieves at least about 90 % yield of dimethyl terephthalate . 39 . The process of claim 1 , wherein the process achieves at least about 95 % yield of dimethyl terephthalate . 40 . The process of claim 1 , wherein the process is performed at atmospheric pressure . * * * * *