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USO09550713B1

(12) United States Patent (10) Patent No.: US 9,550,713 B1


ESSaddam (45) Date of Patent: Jan. 24, 2017
(54) POLYETHYLENE TEREPHTHALATE 5,051,528 A 9/1991 Naujokas et al.
DEPOLYMERIZATION 5,328,982 A 7, 1994 Tindall et al.
6,528,546 B2 3/2003 Lee et al.
6,670.503 B2 12/2003 Broccatelli
(71) Applicant: ep Industries, Los Angeles, CA 6,720,448 B2 4/2004 Broccatelli
(US) 6,911,546 B2 6/2005 Hedrick et al.
6,916,936 B2 7/2005 Hedricket al.
(72) Inventor: Hatem Essaddam, Ste. Therese (CA) 7,053,221 B2 5/2006 Hedrick et al.
7,544,800 B2 6/2009 Hedricket al.
(73) Assignee: LOOP INDUSTRIES, INC., Los S. R:
- W-
388 sity CCCK ( a.
1
Angeles, CA (US) 8,492,504 B2 7/2013 Hedrick et al.
2008/0242751 A1 10, 2008 Kuri tal.
(c ) Notice: Subject to any disclaimer, the term of this 2011 0004014 A1 1/2011 E. a . . . . . . . . . . . . . . CO7C 67.03
patent is extended or adjusted under 35 560.89
(b) by 0O. day
U.S.C. 154(b) dav.S. 2013/0345453 Al 12/2013 Sipos et al.
(21) Appl. No.: 14/795,116 FOREIGN PATENT DOCUMENTS
(22) Filed: L. 9, 2015 CN 10274.6460. A 10, 2012
9 JP 2001.261707 A 9, 2001
JP 4575,074 B2 11 2010
(51) Int. Cl. WO WO-9527753 A1 10, 1995
C07C 5 L/09 (2006.01) WO WO-9724310 A1 T 1997
C07C 29/128 (2006.01) WO WO-9746611 A1 12/1997
C08. II/24 (2006.01) WO WO-98O3459 A1 1, 1998
52) U.S. C WO WO-0047659 A1 8, 2000
( ) AV e. we WO WO-0158982 A1 8, 2001
CPC ........... C07C 51/09 (2013.01); C07C 29/1285 WO WO-0218471 A2 3, 2002
(2013.01); C08.J II/24 (2013.01); C08.J WO WO-O238276 A1 5, 2002
2367/03 (2013.01) WO WO-2005OO3217 A1 1, 2005
WO WO-2006021063 A1 3, 2006
(58) Field of Classification Search WO WO-2007076384 A2 7, 2007
CPC ...... CO7C 51/09; CO7C 29/1285: CO7C 67/03; WO WO-2007O96326 A1 8, 2007
CO7C 231/02: CO7C 69/82: CO7C 68/06; WO WO-2007 113872 A1 10/2007
C07C 69/96; C07C 63/26: C07C 233/64; WO WO-2007 148353 Al 12/2007
Co7C 233/69. Co7C 233/78. Co7C WO WO-2008007384 A1 1/2008
59/285; CO7C 37/64; C07C
39/235; C07C 31/202: C08J 11/24: CO8J OTHER PUBLICATIONS
2367/03; C08J 11/16: C08J Feghali "Room Temperature Organocatalyzed Reductive Polymer
2367/02: C08J 11/00; C08J 11/08: C08J ization of Waster Polyethers Polyesters and Polycarbonates'
2201/03; C08J 2369/00; C08J 2371/00; ChemSusChem 8(6), p. 980-984, first available online Feb. 23.
C08J 9/0085; CO7F 1700; Y02W 30/705; 2015.*
Y02W 30/706; Y02W 30/701; C08G Ramsden “Factors Influencing the Kinetics of the Alkaline
2650/56; C08G 59/50: C08G Depolymerisation of Poly(ethylene terephthalate) I: the Effect of
63/183; C08G 63/85; C08G 64/04; C08L Solvent' J. Chem. Tech. Biotechnol. 1996, 67, 131-136.*
63 FOO CO8L 71 f()0: D21H 17753: D21H Haga "Anomalous Swelling of Poly(ethylene terephthalate) fiber in
19/24: D2H 21/16. D21H 21/18: D21H organic solvents' Journal of Polymer Science, Polymer Letters
1720. yios 264/ois Edition (1982), 29 p. 629-64.
Feghali et al. Room Temperature Organocatalyzed Reductive
USPC ............ 562/483, 485, 480, 486, 487, 308.1; Depolymerization of Waste Polyethers Polyesters and Polycarbon
521/40, 42.5.48, 40.5, 48.5, 49; ates. ChemSusChem. 8(6):980-984 (2015), Feb. 23, 2015.
548/316.7,336.5, 101, 181, 215; 560/78, Venkatachalam et al. Materials Science “Polyester' Chapter 4:
560/216, 79; 134/29, 42:522/90; Degradation and Recyclability of Poly(Ethylene Terephthalate).
523/500: 528/272,308.1, 198, 271, 274, Intech 24pgs. (2012).
528/308.2, 310,480, 481, 485, 488, 489, Haga. Case II Swelling of poly(ethylene terephthalate) in organic
528/493, 495, 497, 503, 86; 544/281, 225, solvents. Journal of Applied Polymer Science 26(8):2649-2655
544/247,279, 280, 282; 564/230. ('').
564/241, 242, 238, 245; 152/315; * cited by examiner
264/918: 502/150, 162: 525/488, 489:
546/2: 549/485; 556/13; 588/80; 568/725, Primary Examiner — Jafar Parsa
568/854, 858, 868, 871 Assistant Examiner — Amy C Bonaparte
See application file for complete search history.
(74) Attorney, Agent, or Firm — Wilson Sonsini Goodrich
(56) References Cited & Rosati
U.S. PATENT DOCUMENTS (57) ABSTRACT
4355.175. A 10, 1982 Puszt The present invention relates to the depolymerization of
5045.22. A 5/1991 ERzer . . . . . . . . . . . . . . B60T 8,348 polymers and the recovery of the starting materials used for
134,29 (Continued)
US 9,550,713 B1
Page 2

the production of the polymer. The present invention also


relates to the depolymerization of polyethylene terephthalate
(PET) and the recovery of terephthalic acid and ethylene
glycol.
19 Claims, No Drawings
US 9,550,713 B1
1. 2
POLYETHYLENE TEREPHTHALATE In another aspect, is a process for depolymerizing poly
DEPOLYMERIZATION mer comprising an ester functionality to starting materials
for use in the production of new polymers, comprising
FIELD OF THE INVENTION admixing the polymer with a mixture of (i) about 3 to about
5% (vol.) of a non-polar solvent capable of swelling the
The present invention relates to the depolymerization of polymer,
solvent;
wherein the non-polar solvent is a halogenated
(ii) about 95 to about 97% (vol.) of a linear C-C,
polymers and the recovery of the starting materials used for
the production of a new polymer. The present invention also alcohol; and (iii) a hydroxide; wherein the admixing is
relates to the depolymerization of polyethylene terephthalate continued for about 1 h; and wherein the process is per
(PET) and the recovery of terephthalic acid and ethylene 10 formed without applying external heat.
In some embodiments, the polymer comprising the ester
glycol. functionality is polyethylene terephthalate and the starting
BACKGROUND OF THE INVENTION
materials for the production of the polymer are terephthalic
acid or salt thereof and ethylene glycol.
In some embodiments, the terephthalic acid or salt thereof
PET recycling methods are categorized into four groups 15 contains less than about 1% impurity (w/w).
namely primary, secondary, tertiary, and quaternary recy In some embodiments, the impurity comprises at least one
cling. of isophthalic acid, phthalic acid, 4-methylbenzoic acid,
SUMMARY OF THE INVENTION
4-formylbenzoic acid, and metals.
2O
In another aspect, is a process for depolymerizing of
In one aspect, is a process for depolymerizing a polymer and ethyleneterephthalate
polyethylene to terephthalic acid or salt thereof
glycol comprising admixing polyethylene
comprising an ester functionality to starting materials for use terephthalate with a mixture of: (i) about 3 to about 5% (vol.)
in the production of new polymers, comprising admixing the of a non-polar solvent capable of Swelling the polymer,
polymer with a mixture of (i) a non-polar solvent capable of wherein the non-polar solvent is a halogenated solvent; (ii)
Swelling the polymer, and (ii) an agent capable of breaking 25
the ester functionality; wherein the admixing is continued about 95 to about 97% (vol.) of a linear C-C alcohol; and
(iii) a hydroxide; wherein the admixing is continued for
for a sufficient time to depolymerize at least a portion of the about 1 h; and wherein the process is performed without
polymer to the starting materials; and wherein the process is applying external heat.
performed without applying external heat.
In some embodiments, the agent capable of breaking the 30 DETAILED DESCRIPTION OF THE
ester functionality is a mixture of an alcohol and a hydrox INVENTION
ide.
In some embodiments, the mixture of the alcohol and the The conversion of many esters to acids and alcohols is
hydroxide is added to the polymer simultaneously with the carried out by boiling the ester in a mixture of base and
non-polar solvent. 35
alcohol. However, the conversion of some esters is very
In some embodiments, the ratio of the non-polar solvent difficult as is the conversion of polyesters to their corre
to alcohol is about 1:10 to about 1:50 (v:v). sponding acids and glycols. Polyesters are normally not
In some embodiments, the polymer is admixed with the soluble in the solvents that are used for the conversion of
non-polar solvent, the hydroxide, and the alcohol for about esters to alcohol and acid. Also, polyesters are often highly
Oh to about 5 h. 40
crystallized, further limiting their solubility and hindering
In some embodiments, the polymer is admixed with the the attack of the ester bonds by a base.
non-polar solvent, the hydroxide, and the alcohol at atmo Polyethylene terephthalate (sometimes written poly(eth
spheric pressure. ylene terephthalate)), commonly abbreviated as PET, is the
In some embodiments, the non-polar solvent capable of most common thermoplastic polymer resin of the polyester
Swelling the polymer is a halogenated solvent. 45
family and is used in fibers for clothing, containers for
In some embodiments, the alcohol is a linear C-C, liquids and foods, thermoforming for manufacturing, and in
alcohol. combination with glass fiber for engineering resins. It is also
In some embodiments, the hydroxide is selected from a referred to by the brand name Mylar R, Decron(R),
group consisting of an alkali metal hydroxide, an alkaline Terylene.R., or Recron(R).
earth metal hydroxide, an ammonium hydroxide, and a 50
The majority of the world’s PET production is for syn
combination thereof. thetic fibers (in excess of 60%), with bottle production
In some embodiments, the polymer is in the form of waste accounting for about 30% of global demand. Polyester
material. makes up about 18% of world polymer production and is the
In some embodiments, the waste material further com third-most-produced polymer; polyethylene (PE) and poly
prises debris that does not include the polymer comprising 55 propylene (PP) are first and second, respectively.
the ester functionality. PET consists of polymerized units of the monomer eth
In some embodiments, the debris comprises at least one of ylene terephthalate, with repeating (CHO) units (For
bottle caps, glue, paper, residual liquid, and dirt. mula I):
In some embodiments, the polymer comprising the ester
functionality is polyethylene terephthalate and the starting 60
materials for the production of the polymer are terephthalic Formula I
acid or salt thereof and ethylene glycol.
In some embodiments, the terephthalic acid or salt thereof
contains less than about 1% impurity (w/w).
In some embodiments, the impurity comprises at least one 65
of isophthalic acid, phthalic acid, 4-methylbenzoic acid,
4-formylbenzoic acid, and metals.
|)-O-( -
US 9,550,713 B1
3 4
Depending on its processing and thermal history, poly monomers or a partial depolymerization to its oligomers and
ethylene terephthalate exists both as an amorphous (trans other industrial chemicals. Since PET is a polyester with
parent) and as a semi-crystalline polymer. The semicrystal functional ester groups, it can be cleaved by some reagents
line material might appear transparent (particle size.<500 Such as water, alcohols, acids, glycols, and amines. Also,
nm) or opaque and white (particle size up to a few microm PET is formed through a reversible polycondensation reac
eters) depending on its crystal structure and particle size. Its tion, so it can be transformed back to its monomer or
monomer bis(2-hydroxyethyl) terephthalate is optionally oligomer units by pushing the reaction to the opposite
synthesized by the esterification reaction between direction through the addition of a condensation product.
terephthalic acid and ethylene glycol with water as a byprod These low molecular products can then be purified and
uct, or by transesterification reaction between ethylene gly 10 reused as raw materials to produce high quality chemical
col and dimethyl terephthalate with methanol as a byprod products (Carta et al., 2003, Environmental Science And
uct. Polymerization is through a polycondensation reaction Pollution Research, Vol. 10, No. 6, pp. 390-394). Among the
of the monomers (done immediately after esterification/ recycling methods, chemical recycling is the most estab
transesterification) with water as the byproduct. lished and the only one acceptable according to the prin
Because PET is an excellent water and moisture barrier 15 ciples of sustainable development, defined as development
material, plastic bottles made from PET are widely used for that meets the needs of present generation without compro
soft drinks. For certain specialty bottles, such as those mising the ability of future generations to meet their needs,
designated for beer containment, PET sandwiches an addi because it leads to the formation of the raw materials
tional polyvinyl alcohol (PVOH) layer to further reduce its (monomers) from which the polymer is originally made. In
oxygen permeability. this way the environment is not surcharged and there is no
Biaxially oriented PET film (often known by one of its need for extra resources for the production of PET. There are
trade names, Mylar R) can be aluminized by evaporating a three main methods in PET chemical recycling depending
thin film of metal onto it to reduce its permeability, and to on the added hydroxyl bearing molecule: glycol for gylco
make it reflective and opaque (MPET). These properties are lysis, methanol for methanolysis, and water for hydrolysis.
useful in many applications, including flexible food pack 25 Other methods include aminolysis and ammonolysis.
aging and thermal insulation. Because of its high mechanical Hydrolysis:
strength, PET film is often used in tape applications, such as Hydrolysis involves the depolymerization of PET to
the carrier for magnetic tape or backing for pressure-sensi terephthalic acid (TPA) and ethylene glycol by the addition
tive adhesive tapes. It is used to make the fabric polar fleece. of water in acidic, alkaline or neutral environment. The
Non-oriented PET sheet can be thermoformed to make 30 hydrolysis products is optionally used to produce virgin
packaging trays and blister packs. When crystallizable PET PET, or is optionally converted to more expensive chemicals
is used, the trays can be used for frozen dinners, since they like oxalic acid (Yoshioka et al., 2003, Ind. Eng. Chem. Res.,
withstand both freezing and oven baking temperatures. As Vol. 42, No. 4, pp. 675-679). Concentrated sulfuric acid is
opposed to amorphous PET, which is transparent, crystal usually used for acid hydrolysis (U.S. Pat. No. 3,952,053;
lizable PET or CPET tends to be black in color. 35 U.S. Pat. No. 4.355,175), caustic soda for alkaline hydro
PET is also used as substrate in thin film and solar cell. lysis (Alter, 1986, Encyclopedia of Polymer Science and
Primary Recycling: Engineering, pp. 103-128, Herman Mark, Wiley Inter
Primary recycling, also known as re-extrusion, is the Science), and water or steam for neutral hydrolysis (Cam
oldest way of recycling PET. It refers to the “in-plant” panelli et al., J. Appl. Polym. Sci., Vol. 48, No. 3, (April
recycling of the scrap materials that have similar features to 40 1993), pp. 443-451 and Campanelli et al., J. Appl. Polym.
the original products. This process ensures simplicity and Sci., Vol. 53, No. 8, (August 1994), pp. 985-991). Hydro
low cost, but requires uncontaminated Scrap, and only deals lysis is slow compared to methanolysis and glycolysis,
with single-type waste, making it an unpopular choice for because among the three depolymerizing agents (i.e. water,
recyclers. methanol, ethylene glycol), water is the weakest nucleop
Secondary Recycling: 45 hile. It also always uses high temperatures or high pressures
Secondary recycling, also known as mechanical recy or a combination thereof. Another disadvantage of hydro
cling, was commercialized in the 1970s. It involves sepa lysis is the difficulty of recovery of the TPA monomer, which
ration of the polymer from its contaminants and reprocess requires numerous steps in order to reach the required purity.
ing it to granules via mechanical means. Mechanical Methanolysis:
recycling steps include Sorting and separation of wastes, 50 Methanolysis is the depolymerization of PET to dimethyl
removal of contaminants, reduction of size by crushing and terephthalate (DMT) and ethylene glycol (EG) by methanol.
grinding, extrusion by heat, and reforming. The more com Glycolysis:
plex and contaminated the waste is, the more difficult it is to Glycolysis is carried out using ethylene glycol to produce
recycle mechanically. Among the main issues of secondary bis(2-hydroxyethyl) terephthalate (BHET) and other PET
recycling are the heterogeneity of the Solid waste, and the 55 glycolyZates, which can be used to manufacture unsaturated
degradation of the product properties each time it is resins, polyurethane foams, copolyesters, acrylic coatings
recycled. Since the reactions in polymerization are all and hydrophobic dystuffs. The BHET produced through
reversible in theory, the employment of heat results to glycolysis can be added with fresh BHET and the mixture
photo-oxidation and mechanical stresses, causing deteriora can be used in any of the two PET production (DMT-based
tion of the product’s properties. Another problem is the 60 or TPA-based) lines. Besides its flexibility, glyclolysis is the
undesirable gray color resulting from the wastes that have simplest, oldest, and least capital-intensive process. Because
the same type of resin, but of different color. of these reasons, much attention has been devoted to the
Tertiary Recycling: glycolysis of PET. Numerous works have been published
Tertiary recycling, more commonly known as chemical about PET glycolysis, wherein the reaction has been con
recycling, involves the transformation of the PET polymer 65 ducted in a wide range of temperature and time.
chain. Usually by means of Solvolytic chain cleavage, this Studies on the kinetics of PET glycolysis have shown that
process can either be a total depolymerization back to its glycolysis without a catalyst (Such as metal salts, Zeolites, or
US 9,550,713 B1
5 6
ionic liquids) is very slow and complete depolymerization of col, polytetramethylene glycol, pentaerythritol. 2.2-bis(4-B-
PET to BHET cannot be achieved. It also yields an end hydroxyethoxyphenyl)propane, and a combination thereof.
product that contains significant amount of other oligomers In some embodiments, the process of the present inven
in addition to the BHET monomer. This results in difficulty tion is useful for the depolymerization of polyethylene
in recovering the BHET monomer when it is the desired 5 terephthalate in whatever form, such as bulk waste material,
product. Thus, research efforts have been directed towards since the conversion is rapid and does not require a grinding
increasing the rate and BHET monomer yield by developing step. In some embodiments, the waste material is washed
highly efficient catalysts and other techniques, and optimiz prior to the depolymerization. In some embodiments, the
ing the reaction conditions (e.g. temperature, time, PET/EG waste material is not washed prior to the depolymerization.
ratio, PET/catalyst ratio). 10 In some embodiments, polymer flakes are used. In some
Quaternary Recycling: embodiments, polyethylene terephthalate is mixed in with
Quaternary recycling represents the recovery of energy debris, such as, but not limited to, bottle caps, glue, paper,
content from the plastic waste by incineration. When the residual liquid, dirt, or a combination thereof.
collection, sorting and separation of plastics waste are In some embodiments, the process of the present inven
15 tion is useful for the selective depolymerization of polymers
difficult or economically not viable, or the waste is toxic and comprising an ester functionality wherein the polymer com
hazardous to handle, the best waste management option is prising an ester functionality is mixed with other polymers
incineration to recover the chemical energy stored in plastics Such as, for example, but not limited to, polyethylene, high
waste in the form of thermal energy. However, it is thought density polyethylene, low density polyethylene, polypropyl
to be ecologically unacceptable due to potential health risks ene, or a combination thereof.
from the air born toxic substances. In some embodiments, the process of the present inven
An Improvement in PET Recycling tion is useful for the selective depolymerization of polyeth
Due to the growing use of polyethylene terephthalate in ylene terephthalate wherein polyethylene terephthalate is
the packaging and fiber (carpet and other textile) industries mixed with other polymers such as, for example, but not
there is a need for an efficient, low energy, high yielding, and 25 limited to, polyethylene, high density polyethylene, low
cost effective way to depolymerize polyethylene terephtha density polyethylene, polypropylene, or a combination
late to generate terephthalic acid and ethylene glycol in thereof.
order to regenerate polyethylene terephthalate. In some embodiments, the process of the present inven
In some embodiments, the process of the present inven tion is useful for depolymerizing a polymer comprising an
tion is useful for the depolymerization of polymers com 30 ester functionality to starting materials for use in the pro
prising an ester functionality in whatever form, Such as bulk duction of new polymers, comprising admixing the polymer
waste material, since the conversion is rapid and does not with a mixture of (i) a non-polar solvent capable of swelling
require a grinding step. In some embodiments, polymer the polymer, and (ii) an agent capable of breaking the ester
flakes are used. In some embodiments, the polymers are functionality; wherein the admixing is continued for a
mixed in with debris, such as, but not limited to, bottle caps, 35 sufficient time to depolymerize at least a portion of the
glue, paper, residual liquid, dirt, or a combination thereof. polymer to the starting materials; and wherein the process is
In some embodiments, the polymer comprising an ester performed without applying external heat.
functionality is selected from polyethylene terephthalate In some embodiments, the non-polar solvent is a solvent
(PET), polyglycolide or polyglycolic acid (PGA), polylactic capable of breaking hydrogen bonds in the polymers. In
acid (PLA), polycaprolactone (PCL), polyhydroxyalkanoate 40 Some embodiments, the non-polar solvent is capable of
(PHA), polyhydroxybutyrate (PHB), polyethylene adipate Swelling the polymers. In some embodiments, the non-polar
(PEA), polybutylene succinate (PBS), poly(3-hydroxybu Solvent is capable of dissolving the polymers. In some
tyrate-co-3-hydroxyvalerate) (PHBV), polybutylene embodiments, the non-polar solvent is an aprotic non-polar
terephthalate (PBT), polytrimethylene terephthalate (PTT), Solvent. In some embodiments, the non-polar solvent is a
polyethylene naphthalate (PEN), vectran, and a combination 45 halogenated solvent. In some embodiments, the non-polar
thereof. Solvent is a chlorinated solvent. In some embodiments, the
In some embodiments, the polymer comprising an ester non-polar solvent is dichloromethane, dichloroethane, tet
functionality is polyethylene terephthalate (PET). rachloroethane, chloroform, tetrachloromethane, trichlo
In some embodiments, the polymer comprising an ester roethane, or a combinations thereof.
functionality is a terephthalic acid/ethylene glycol oligomer. 50 In some embodiments, the agent capable of breaking the
In some embodiments, the polymer comprising an ester ester functionality is a mixture of an alcohol and a base. In
functionality is a dicarboxylic acid/dialcohol oligomer, Some embodiments, the agent capable of breaking the ester
wherein the dicarboxylic acid is selected from the group functionality is a mixture of an alcohol and an acid.
consisting of naphthalene dicarboxylic acid, diphenyldicar In some embodiments, the alcohol used in the agent
boxylic acid, diphenyl ether dicarboxylic acid, diphenylsul 55 capable of breaking the ester functionality is an alcohol that
fonedicarboxylic acid, diphenoxyethanedicarboxylic acid, is capable of dissolving the base. In some embodiments the
Succinic acid, adipic acid, sebacic acid, azelaic acid, alcohol is a linear, branched, cyclic alcohol, or a combina
decanedicarboxylic acid, cyclohexanedicarboxylic acid, tion thereof. In some embodiments, the alcohol is a linear
trimelitic acid, pyromellitic acid, and a combination C-C alcohol. In some embodiments, the alcohol is metha
thereof, and the dialcohol is selected from the group con 60 nol, ethanol, propanol, butanol, or a combination thereof. In
sisting of trimethylene glycol, 1,2-propanediol, tetrameth Some embodiments, the alcohol is methanol, ethanol, pro
ylene glycol, neopentyl glycol, hexamethylene glycol, panol, or a combination thereof. In some embodiments, the
decanemethylene glycol, dodecamethylene glycol, 1.4-cy alcohol is methanol. In some embodiments, the alcohol is
clohexanedimethanol, diethylene glycol, triethylene glycol, ethanol. In some embodiments, the alcohol is a branched
tetraethylene glycol, polyethylene glycol, dipropylene gly 65 C-C alcohol. In some embodiments, the alcohol is t-buta
col, tripropylene glycol, tetrapropylene glycol, polypropyl nol, S-butanol, i-butanol, i-propanol, S-propanol, or a com
ene glycol, di(tetramethylene)glycol, tri(tetramethylene)gly bination thereof. In some embodiments, the alcohol is a
US 9,550,713 B1
7 8
cyclic C-C alcohol. In some embodiments, the alcohol is solvent. In some embodiments, the mixture of the alcohol
cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, and the hydroxide is added to the polymer simultaneously
cycloheptanol, or a combination thereof. with the non-polar solvent. In some embodiments, the
In some embodiments, the base used in the agent capable mixture of the alcohol and the alkoxide is added to the
of breaking the ester functionality is a base that is Substan polymer simultaneously with the non-polar solvent. In some
tially soluble in the final solution. embodiments the base is dissolved in the alcohol prior to the
In some embodiments, the base capable of breaking the addition to the non-polar solvent.
ester functionality is an alkoxide. In some embodiments, the In some embodiments, the ratio of the non-polar solvent
alkoxide is a C-C alkoxide. In some embodiments, the to alcohol is from about 1:1 (v:v) to about 1:100 (v:v). In
alkoxide is selected from a group consisting of methoxide, 10 Some embodiments, the ratio of the non-polar solvent to
ethoxide, n-propoxide, n-butoxide, t-butoxide, S-butoxide, alcohol is from about 1:1 (v:v) to about 1:10 (v:v). In some
i-butoxide, i-propoxide, S-propoxide, and a combination embodiments, the ratio of the non-polar solvent to alcohol is
thereof. In some embodiments, the alkoxide is methoxide, from about 1:10 (v:v) to about 1:20 (v:v). In some embodi
ethoxide, or a combination thereof. ments, the ratio of the non-polar solvent to alcohol is from
In some embodiments, the base capable of breaking the 15 about 1:20 (v:v) to about 1:30 (v:v). In some embodiments,
ester functionality is a hydroxide. In some embodiments, the the ratio of the non-polar solvent to alcohol is from about
hydroxide is selected from the group consisting of alkali 1:30 (v:v) to about 1:40 (v:v). In some embodiments, the
metal hydroxide, alkaline-earth metal hydroxide, and ratio of the non-polar solvent to alcohol is from about 1:40
ammonium hydroxide, and a combination thereof. In some (v:v) to about 1:50 (v:v). In some embodiments, the ratio of
embodiments, the hydroxide is selected from a group con the non-polar solvent to alcohol is from about 1:50 (v:v) to
sisting of sodium hydroxide, potassium hydroxide, calcium about 1:60 (v:v). In some embodiments, the ratio of the
hydroxide, lithium hydroxide, magnesium hydroxide, non-polar solvent to alcohol is from about 1:60 (v:v) to
ammonium hydroxide, tetra-alkyl ammonium hydroxide, about 1:70 (v:v). In some embodiments, the ratio of the
and a combination thereof. In some embodiments, the non-polar solvent to alcohol is from about 1:70 (v:v) to
hydroxide is sodium hydroxide, potassium hydroxide, or a 25 about 1:80 (v:v). In some embodiments, the ratio of the
combination thereof. In some embodiments, the hydroxide is non-polar solvent to alcohol is from about 1:80 (v:v) to
sodium hydroxide. In some embodiments, the hydroxide is about 1:90 (v:v). In some embodiments, the ratio of the
potassium hydroxide. In some embodiments, the hydroxide non-polar solvent to alcohol is from about 1:90 (v:v) to
is a mixture of sodium hydroxide and potassium hydroxide. about 1:100 (v:v). In some embodiments, the ratio of the
In some embodiments, the acid used in the agent capable 30 non-polar solvent to alcohol is from about 1:1 (v:v) to about
of breaking the ester functionality is an organic acid. In some 1:50 (v:v). In some embodiments, the ratio of the non-polar
embodiments, the acid used in the agent capable of breaking solvent to alcohol is from about 1:2 (v:v) to about 1:50 (v:v).
the ester functionality is an inorganic acid. In some embodi In some embodiments, the ratio of the non-polar solvent to
ments, the acid is Sulfuric acid, hydrochloric acid, or a alcohol is from about 1:3 (v:v) to about 1:50 (v:v). In some
combination thereof. 35 embodiments, the ratio of the non-polar solvent to alcohol is
In some embodiments, the molar ratio of base or acid to from about 1:4 (v:v) to about 1:50 (v:v). In some embodi
the ester bonds present in the polymer is greater than 1:1. In ments, the ratio of the non-polar solvent to alcohol is from
some embodiments, the molar ratio of base to the ester about 1:5 (v:v) to about 1:50 (v:v). In some embodiments,
bonds present in the polymer is greater than 1:1. In some the ratio of the non-polar solvent to alcohol is from about 1:6
embodiments, the molar ratio of hydroxide to the ester bonds 40 (v:v) to about 1:50 (v:v). In some embodiments, the ratio of
present in the polymer is greater than 1:1. In some embodi the non-polar solvent to alcohol is from about 1:7 (v:v) to
ments, the molar ratio of alkoxide to the ester bonds present about 1:50 (v:v). In some embodiments, the ratio of the
in the polymer is greater than 1:1. In some embodiments, the non-polar solvent to alcohol is from about 1:8 (v:v) to about
molar ratio of base or acid to the ester bonds present in the 1:50 (v:v). In some embodiments, the ratio of the non-polar
polymer is lower than 1:1. In some embodiments, the molar 45 solvent to alcohol is from about 1:9 (v:v) to about 1:50 (v:v).
ratio of base to the ester bonds present in the polymer is In some embodiments, the ratio of the non-polar solvent to
lower than 1:1. In some embodiments, the molar ratio of alcohol is from about 1:10 (v:v) to about 1:50 (v:v). In some
hydroxide to the ester bonds present in the polymer is lower embodiments, the ratio of the non-polar solvent to alcohol is
than 1:1. In some embodiments, the molar ratio of alkoxide about 1:10 (v:v), about 1:11 (v:v), about 1:12 (v:v), about
to the ester bonds present in the polymer is lower than 1:1. 50 1:13 (v:v), about 1:14 (v:v), about 1:15 (v:v), about 1:16
In some embodiments, the molar ratio of base or acid to the (v:v), about 1:17 (v:v), about 1:18 (v:v), about 1:19 (v:v),
ester bonds present in the polymer is about 1:1. In some about 1:20 (v:v), about 1:21 (v:v), about 1:22 (v:v), about
embodiments, the molar ratio of base to the ester bonds 1:23 (v:v), about 1:24 (V:V), about 1:25 (v:v), about 1:26
present in the polymer is about 1:1. In some embodiments, (v:v), about 1:27 (v:v), about 1:28 (v:v), about 1:29 (v:v),
the molar ratio of hydroxide to the ester bonds present in the 55 about 1:30 (v:v), about 1:31 (v:v), about 1:32 (v:v), about
polymer is about 1:1. In some embodiments, the molar ratio 1:33 (viv), about 1:34 (v:v), about 1:35 (v:v), about 1:36
of alkoxide to the ester bonds present in the polymer is about (v:v), about 1:37 (v:v), about 1:38 (v:v), about 1:39 (v:v),
1:1. about 1:40 (v:v), about 1:41 (v:v), about 1:42 (v:v), about
In some embodiments, the mixture of the alcohol and the 1:43 (v:v), about 1:44 (V:V), about 1:45 (v:v), about 1:46
base or acid is added to the polymer prior to the addition of 60 (v:v), about 1:47 (v:v), about 1:48 (v:v), about 1:49 (v:v), or
the non-polar solvent. In some embodiments, the mixture of about 1:50 (v:v).
the alcohol and the base or acid is added to the polymer after In some embodiments, the amount of alcohol is from
the addition of the non-polar solvent. In some embodiments, about 70% to about 99% (vol.) of the total mixture volume.
the mixture of the alcohol and the base or acid is added to In some embodiments, the amount of alcohol is from about
the polymer simultaneously with the non-polar solvent. In 65 95% to about 97% (vol.) of the total mixture volume. In
some embodiments, the mixture of the alcohol and the base some embodiments, the amount of alcohol is about 70%
is added to the polymer simultaneously with the non-polar (vol.), about 71% (vol.), about 72% (vol.), about 73% (vol.),
US 9,550,713 B1
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about 74% (vol.), about 75% (vol.), about 76% (vol.), about In some embodiments, the process of the present inven
77% (vol.), about 78% (vol.), about 79% (vol.), about 80% tion is conducted at atmospheric pressure. In some embodi
(vol.), about 81% (vol.), about 82% (vol.), about 83% (vol.), ments, the process of the present invention is conducted at
about 84% (vol.), about 85% (vol.), about 86% (vol.), about elevated pressures. In some embodiments, the process of the
87% (vol.), about 88% (vol.), about 89% (vol.), about 90% present invention is conducted at a pressure between about
(vol.), about 91% (vol.), about 92% (vol.), about 93% (vol.), atmospheric and about 220 psi. In some embodiments, the
about 94% (vol.), about 95% (vol.), about 96% (vol.), about process of the present invention is conducted at about 14 psi,
97% (vol.), about 98% (vol.), or about 99% (vol.) of the total about 15 psi, about 16 psi, about 17 psi, about 18 psi, about
mixture Volume. 19 psi, about 20 psi, about 30 psi, about 40 psi, about 50 psi,
In some embodiments, the amount of non-polar solvent is 10 about 60 psi, about 70 psi, about 80 psi, about 90 psi, about
from about 1% to about 30% (vol.) of the total mixture 100 psi, about 110 psi, about 120 psi, about 130 psi, about
Volume. In some embodiments, the amount of non-polar 140 psi, about 150 psi, about 160 psi, about 170 psi, about
solvent is from about 3% to about 5% (vol.) of the total 180 psi, about 190 psi, about 200 psi, about 210 psi, or about
mixture Volume. In some embodiments, the amount of 220 psi.
non-polar solvent is about 1% (vol.), about 2% (vol.), about 15 In some embodiments, the process of the present inven
3% (vol.), about 4% (vol.), about 5% (vol.), about 6% (vol.), tion is conducted without agitation. In some embodiments,
about 7% (vol.), about 8% (vol.), about 9% (vol.), about the process of the present invention is conducted with
10% (vol.), 11% (vol.), about 12% (vol.), about 13% (vol.), increased agitation. In some embodiments, a stirred batch
about 14% (vol.), about 15% (vol.), about 16% (vol.), about reactor is used to provide agitation. In some embodiments,
17% (vol.), about 18% (vol.), about 19% (vol.), about 20% a continuous reactor is used to provide agitation.
(vol.), 21% (vol.), about 22% (vol.), about 23% (vol.), about In some embodiments, the process of the present inven
24% (vol.), about 25% (vol.), about 26% (vol.), about 27% tion is conducted without the addition of a catalyst. In some
(vol.), about 28% (vol.), about 29% (vol.), or about 30% embodiments, the process of the present invention is con
(vol.) of the total mixture volume. ducted with the addition of a catalyst. In some embodiments,
In some embodiments, the polymer is admixed with the 25 the catalyst used in the depolymerization process of the
non-polar solvent and the agent capable of breaking the ester present invention comprises at least one of germanium
functionality for a sufficient time to depolymerize at least a compounds, titanium compounds, antimony compounds,
portion of the polymer to the starting materials for the Zinc compounds, cadmium compounds, manganese com
production of the polymer. pounds, magnesium compounds, cobalt compounds, silicon
In some embodiments, the depolymerization is instanta 30 compounds, tin compounds, lead compounds, and aluminum
neous. In some embodiments, the Sufficient time to depo compounds.
lymerize at least a portion of the polymer to the starting In some embodiments, the catalyst used in the depolymer
materials for the production of new polymer is about 0h to ization process of the present invention comprises at least
about 24 h. In some embodiments, the sufficient time to one of germanium dioxide, cobalt acetate, titanium tetra
depolymerize at least a portion of the polymer to the starting 35 chloride, titanium phosphate, titanium tetrabutoxide, tita
materials for use in the production of new polymers is about nium tetraisopropoxide, titanium tetra-n-propoxide, tita
Oh to about 20h, about 0h to about 15 h, about 0h to about nium tetraethoxide, titanium tetramethoxide, a tetrakis
10 h, Oh to about 5 h, about 0 h to about 4 h, about 0 h to (acetylacetonato) titanium complex, a tetrakis(2,4-
about 3 h, about 0h to about 2 h, or about 0h to about 1 h. hexanedionato) titanium complex, a tetrakis(3,5-
In some embodiments, the Sufficient time to depolymerize at 40 heptanedionato)titanium complex, a dimethoxybis
least a portion of the polymer to the starting materials for the (acetylacetonato) titanium complex, a diethoxybis
production of the polymer is about Oh, 0.1 h, 0.2 h, 0.3 h. (acetylacetonato) titanium complex, a diisopropoxybis
about 0.4 h, about 0.5 h, about 0.6 h, about 0.7 h, about 0.8 (acetylacetonato) titanium complex, a di-n-propoxybis
h, about 0.9 h, or about 1 h. (acetylacetonato) titanium complex, a dibutoxybis
In some embodiments, the process of the present inven 45 (acetylacetonato) titanium complex, titanium
tion is conducted at ambient temperature. In some embodi dihydroxybisglycolate, titanium dihydroxybislactate, tita
ments, ambient temperature is 25+5° C. nium dihydroxybis(2-hydroxypropionate), titanium lactate,
In some embodiments, the process of the present inven titanium octanediolate, titanium dimethoxybistriethanol
tion is conducted without applying external heat. In some aminate, titanium diethoxybistriethanol aminate, titanium
embodiments, the reaction is exothermic and the tempera 50 dibutoxybistriethanol aminate, hexamethyl dititanate, hexa
ture of the reaction mixture rises to at least 30° C., at least ethyl dititanate, hexapropyl dititanate, hexabutyl dititanate,
35°C., at least 40°C., at least 45° C., at least 50° C., at least hexaphenyldititanate, octamethyl trititanate, octaethyl triti
55° C., or even at least 60° C. In some embodiments, no tanate, octapropyl trititanate, octabutyl trititanate, octaphe
external heat sources are used to increase the temperature of nyl trititanate, a hexaalkoxy dititanate, Zinc acetate, manga
the reaction mixture. 55 nese acetate, methyl silicate, Zinc chloride, lead acetate,
In some embodiments, the process of the present inven Sodium carbonate, sodium bicarbonate, acetic acid, sodium
tion is conducted with external heat. In some embodiments, Sulfate, potassium sulfate, Zeolites, lithium chloride, mag
the process of the present invention is conducted with nesium chloride, ferric chloride, Zinc oxide, magnesium
external heat at between about 20° C. and about 100° C. In oxide, calcium oxide, barium oxide, antimony trioxide, and
Some embodiments, the process of the present invention is 60 antimony triacetate.
conducted at about 20°C., about 21°C., about 22°C., about In some embodiments, the process of the present inven
23°C., about 24°C., about 25°C., about 26°C., about 27° tion is useful for depolymerizing a polymer comprising an
C., about 28°C., about 29° C., about 30° C., about 35° C., ester functionality to starting materials for use in the pro
about 40°C., about 45° C., about 50° C., about 55° C., about duction of new polymers comprising admixing the polymer
60° C., about 65° C., about 70° C., about 75° C., about 80° 65 with a mixture of (i) about 3 to about 5% (vol.) of a
C., about 85°C., about 90° C., about 95°C., or about 100° non-polar solvent capable of Swelling the polymer, wherein
C. the non-polar solvent is a chlorinated solvent; (ii) about 95
US 9,550,713 B1
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to about 97% (vol.) of a linear C-C alcohol; and (iii) a In some embodiments, the starting materials for use in the
hydroxide; wherein the admixing is continued for about 1 h; production of new polymers obtained from depolymerizing
and wherein the process is performed without applying a polymer comprising an ester functionality contain less than
external heat. about 10% impurity (w/w). In some embodiments, the
In some embodiments, the polymer comprising an ester starting materials for use in the production of new polymers
functionality is polyethylene terephthalate. In some embodi obtained from depolymerizing a polymer comprising an
ments, the starting materials for use in the production of new ester functionality contain less than about 9% impurity
polymers is selected from the group consisting of (w/w). In some embodiments, the starting materials for use
terephthalic acid/ethylene glycol oligomers or salt thereof, in the production of new polymers obtained from depo
terephthalic acid or salt thereof, 4-(methoxycarbonyl)ben 10 lymerizing a polymer comprising an ester functionality
Zoic acid or a salt thereof, ethylene glycol, and a combina contain less than about 8% impurity (w/w). In some embodi
tion thereof. ments, the starting materials for use in the production of new
polymers obtained from depolymerizing a polymer compris
In some embodiments, the starting materials for use in the ing an ester functionality contain less than about 7% impu
production of new polymers are terephthalic acid or salt 15 rity (w/w). In some embodiments, the starting materials for
thereof and ethylene glycol. use in the production of new polymers obtained from
In some embodiments, the starting materials for use in the depolymerizing a polymer comprising an ester functionality
production of new polymers are 4-(methoxycarbonyl)ben contain less than about 6% impurity (w/w). In some embodi
Zoic acid or salt thereof and ethylene glycol. ments, the starting materials for use in the production of new
In some embodiments, the starting materials for use in the polymers obtained from depolymerizing a polymer compris
production of new polymers are terephthalic acid/ethylene ing an ester functionality contain less than about 5% impu
glycol oligomers. rity (w/w). In some embodiments, the starting materials for
In some embodiments, the process of the present inven use in the production of new polymers obtained from
tion is useful for depolymerizing polyethylene terephthalate depolymerizing a polymer comprising an ester functionality
to terephthalic acid or salt thereof and ethylene glycol 25 contain less than about 4% impurity (w/w). In some embodi
comprising admixing polyethylene terephthalate with a mix ments, the starting materials for use in the production of new
ture of (i) a non-polar solvent capable of Swelling the polymers obtained from depolymerizing a polymer compris
polymer; and (ii) an agent capable of breaking the ester ing an ester functionality contain less than about 3% impu
functionality; wherein the admixing is continued for a rity (w/w). In some embodiments, the starting materials for
Sufficient time to depolymerize at least a portion of poly 30 use in the production of new polymers obtained from
ethylene terephthalate to terephthalic acid or salt thereof and depolymerizing a polymer comprising an ester functionality
ethylene glycol; and wherein the process is performed contain less than about 2% impurity (w/w). In some embodi
without applying external heat. ments, the starting materials for use in the production of new
In some embodiments, the process of the present inven polymers obtained from depolymerizing a polymer compris
tion is useful for depolymerizing polyethylene terephthalate 35 ing an ester functionality contain less than about 1% impu
to 4-(methoxycarbonyl)benzoic acid or salt thereof and rity (w/w). In some embodiments, the starting materials for
ethylene glycol comprising admixing polyethylene use in the production of new polymers obtained from
terephthalate with a mixture of (i) a non-polar solvent depolymerizing a polymer comprising an ester functionality
capable of Swelling the polymer, and (ii) an agent capable of contain less than about 0.5% impurity (w/w). In some
breaking the ester functionality; wherein the admixing is 40 embodiments, the starting materials for use in the production
continued for a sufficient time to depolymerize at least a of new polymers obtained from depolymerizing a polymer
portion of polyethylene terephthalate to 4-(methoxycarbo comprising an ester functionality contain less than about
nyl)benzoic acid or salt thereof and ethylene glycol; and 0.4% impurity (w/w). In some embodiments, the starting
wherein the process is performed without applying external materials for use in the production of new polymers obtained
heat. 45 from depolymerizing a polymer comprising an ester func
In some embodiments, the process of the present inven tionality contain less than about 0.3% impurity (w/w). In
tion is useful for depolymerizing polyethylene terephthalate Some embodiments, the starting materials for use in the
to terephthalic acid or salt thereof and ethylene glycol production of new polymers obtained from depolymerizing
comprising admixing polyethylene terephthalate with a mix a polymer comprising an ester functionality contain less than
ture of (i) about 3 to about 5% (vol.) of a non-polar solvent 50 about 0.2% impurity (w/w). In some embodiments, the
capable of swelling polyethylene terephthalate, wherein the starting materials for use in the production of new polymers
non-polar solvent is a chlorinated solvent; (ii) about 95 to obtained from depolymerizing a polymer comprising an
about 97% (vol.) of a linear C-C alcohol; and (iii) a ester functionality contain less than about 0.1% impurity
hydroxide; wherein the admixing is continued for about 1 h; (w/w).
and wherein the process is performed without applying 55 In some embodiments, terephthalic acid or salt thereof
external heat. contains less than about 10% impurity (w/w). In some
In some embodiments, the process of the present inven embodiments, terephthalic acid or salt thereof contains less
tion is useful for depolymerizing polyethylene terephthalate than about 9% impurity (w/w). In some embodiments,
to 4-(methoxycarbonyl)benzoic acid or salt thereof and terephthalic acid or salt thereof contains less than about 8%
ethylene glycol comprising admixing polyethylene 60 impurity (w/w). In some embodiments, terephthalic acid or
terephthalate with a mixture of (i) about 3 to about 5% (vol.) salt thereof contains less than about 7% impurity (w/w). In
of a non-polar solvent capable of Swelling polyethylene Some embodiments, terephthalic acid or salt thereof contains
terephthalate, wherein the non-polar solvent is a chlorinated less than about 6% impurity (w/w). In some embodiments,
solvent; (ii) about 95 to about 97% (vol.) of a linear C-C, terephthalic acid or salt thereof contains less than about 5%
alcohol; and (iii) a hydroxide; wherein the admixing is 65 impurity (w/w). In some embodiments, terephthalic acid or
continued for about 1 h; and wherein the process is per salt thereof contains less than about 4% impurity (w/w). In
formed without applying external heat. Some embodiments, terephthalic acid or salt thereof contains
US 9,550,713 B1
13 14
less than about 3% impurity (w/w). In some embodiments, In some embodiments, the impurity contained in the
terephthalic acid or salt thereof contains less than about 2% starting materials for use in the production of new polymers
impurity (w/w). In some embodiments, terephthalic acid or obtained from depolymerizing polyethylene terephthalate
salt thereof contains less than about 1% impurity (w/w). In comprises at least one of isophthalic acid, phthalic acid,
Some embodiments, terephthalic acid or salt thereof contains 4-methylbenzoic acid, and 4-formylbenzoic acid.
less than about 0.5% impurity (w/w). In some embodiments, In some embodiments, the starting materials for use in the
terephthalic acid or salt thereof contains less than about production of new polymers obtained from depolymerizing
0.4% impurity (w/w). In some embodiments, terephthalic polyethylene terephthalate contains less than about 100 ppm
acid or salt thereof contains less than about 0.3% impurity of 4-formylbenzoic acid, less than about 90 ppm of 4-form
(w/w). In some embodiments, terephthalic acid or salt 10 ylbenzoic acid, less than about 80 ppm of 4-formylbenzoic
thereof contains less than about 0.2% impurity (w/w). In acid, less than about 70 ppm of 4-formylbenzoic acid, less
Some embodiments, terephthalic acid or salt thereof contains than about 60 ppm of 4-formylbenzoic acid, less than about
50 ppm of 4-formylbenzoic acid, less than about 40 ppm of
less than about 0.1% impurity (w/w). 4-formylbenzoic acid, less than about 30 ppm of 4-formyl
In some embodiments, 4-(methoxycarbonyl)benzoic acid 15 benzoic acid, less than about 20 ppm of 4-formylbenzoic
or salt thereof contains less than about 10% impurity (w/w). acid, or less than about 10 ppm of 4-formylbenzoic acid.
In some embodiments, 4-(methoxycarbonyl)benzoic acid or In some embodiments, the starting materials for use in the
salt thereof contains less than about 9% impurity (w/w). In production of new polymers obtained from depolymerizing
Some embodiments, 4-(methoxycarbonyl)benzoic acid or polyethylene terephthalate contains less than about 200 ppm
salt thereof contains less than about 8% impurity (w/w). In of 4-methylbenzoic acid, less than about 190 ppm of 4-meth
Some embodiments, 4-(methoxycarbonyl)benzoic acid or ylbenzoic acid, less than about 180 ppm of 4-methylbenzoic
salt thereof contains less than about 7% impurity (w/w). acid, less than about 170 ppm of 4-methylbenzoic acid, less
Some embodiments, 4-(methoxycarbonyl)benzoic acid than about 160 ppm of 4-methylbenzoic acid, less than about
salt thereof contains less than about 6% impurity (w/w). 150 ppm of 4-methylbenzoic acid, less than about 140 ppm
Some embodiments, 4-(methoxycarbonyl)benzoic acid 25 of 4-methylbenzoic acid, less than about 130 ppm of 4-meth
salt thereof contains less than about 5% impurity (w/w). ylbenzoic acid, less than about 120 ppm of 4-methylbenzoic
Some embodiments, 4-(methoxycarbonyl)benzoic acid acid, less than about 110 ppm of 4-methylbenzoic acid, less
salt thereof contains less than about 4% impurity (w/w). than about 100 ppm of 4-methylbenzoic acid, less than about
Some embodiments, 4-(methoxycarbonyl)benzoic acid 90 ppm of 4-methylbenzoic acid, less than about 80 ppm of
salt thereof contains less than about 3% impurity (w/w). 30 4-methylbenzoic acid, less than about 70 ppm of 4-methyl
Some embodiments, 4-(methoxycarbonyl)benzoic acid benzoic acid, less than about 60 ppm of 4-methylbenzoic
salt thereof contains less than about 2% impurity (w/w). acid, less than about 50 ppm of 4-methylbenzoic acid, less
Some embodiments, 4-(methoxycarbonyl)benzoic acid than about 40 ppm of 4-methylbenzoic acid, less than about
salt thereof contains less than about 1% impurity (w/w). 30 ppm of 4-methylbenzoic acid, less than about 20 ppm of
Some embodiments, 4-(methoxycarbonyl)benzoic acid 35 4-methylbenzoic acid, or less than about 10 ppm of 4-meth
salt thereof contains less than about 0.5% impurity (w/w). ylbenzoic acid.
Some embodiments, 4-(methoxycarbonyl)benzoic acid or In some embodiments, the impurity contained in the
salt thereof contains less than about 0.4% impurity (w/w). In starting materials for use in the production of new polymers
Some embodiments, 4-(methoxycarbonyl)benzoic acid or obtained from depolymerizing polyethylene terephthalate
salt thereof contains less than about 0.3% impurity (w/w). In 40 comprises metals. In some embodiments, the metal impurity
Some embodiments, 4-(methoxycarbonyl)benzoic acid or comprises at least one of aluminum, arsenic, calcium, cobalt,
salt thereof contains less than about 0.2% impurity (w/w). In chromium, iron, potassium, manganese, molybdenum,
Some embodiments, 4-(methoxycarbonyl)benzoic acid or Sodium, nickel, titanium, and lead.
salt thereof contains less than about 0.1% impurity (w/w). In some embodiments, the starting materials for use in the
In some embodiments, ethylene glycol obtained contains 45 production of new polymers obtained from depolymerizing
less than about 10% impurity (w/w). In some embodiments, polyethylene terephthalate contains less than about 250 ppm
ethylene glycol contains less than about 9% impurity (w/w). of any metals, less than about 240 ppm of any metals, less
In some embodiments, ethylene glycol contains less than than about 230 ppm of any metals, less than about 220 ppm
about 8% impurity (w/w). In some embodiments, ethylene of any metals, less than about 210 ppm of any metals, less
glycol contains less than about 7% impurity (w/w). In some 50 than about 200 ppm of any metals, less than about 190 ppm
embodiments, ethylene glycol contains less than about 6% of any metals, less than about 180 ppm of any metals, less
impurity (w/w). In some embodiments, ethylene glycol than about 170 ppm of any metals, less than about 160 ppm
contains less than about 5% impurity (w/w). In some of any metals, less than about 150 ppm of any metals, less
embodiments, ethylene glycol contains less than about 4% than about 140 ppm of any metals, less than about 130 ppm
impurity (w/w). In some embodiments, ethylene glycol 55 of any metals, less than about 120 ppm of any metals, less
contains less than about 3% impurity (w/w). In some than about 110 ppm of any metals, less than about 100 ppm
embodiments, ethylene glycol contains less than about 2% of any metals, less than about 90 ppm of any metals, less
impurity (w/w). In some embodiments, ethylene glycol than about 80 ppm of any metals, less than about 70 ppm of
contains less than about 1% impurity (w/w). In some any metals, less than about 60 ppm of any metals, less than
embodiments, ethylene glycol contains less than about 0.5% 60 about 50 ppm of any metals, less than about 40 ppm of any
impurity (w/w). In some embodiments, ethylene glycol metals, less than about 30 ppm of any metals, less than about
contains less than about 0.4% impurity (w/w). In some 20 ppm of any metals, less than about 10 ppm of any metals,
embodiments, ethylene glycol contains less than about 0.3% less than about 5 ppm of any metals, less than about 4 ppm
impurity (w/w). In some embodiments, ethylene glycol of any metals, less than about 3 ppm of any metals, less than
contains less than about 0.2% impurity (w/w). In some 65 about 2 ppm of any metals, less than about 1 ppm of any
embodiments, ethylene glycol contains less than about 0.1% metals, less than about 0.9 ppm of any metals, less than
impurity (w/w). about 0.8 ppm of any metals, less than about 0.7 ppm of any
US 9,550,713 B1
15 16
metals, less than about 0.6 ppm of any metals, less than In some embodiments, the stabilizer present in the starting
about 0.5 ppm of any metals, less than about 0.4 ppm of any polymer comprising an ester functionality comprises a phos
metals, less than about 0.3 ppm of any metals, less than phate, a phosphonate, and a phosphite compound. In some
about 0.2 ppm of any metals, less than about 0.1 ppm of any embodiments, the stabilizer present in the starting polymer
metals, less than about 0.09 ppm of any metals, less than 5 comprising an ester functionality comprises at least one of
about 0.08 ppm of any metals, less than about 0.07 ppm of polyphosphoric acid, phosphoric acid, organophosphorus
any metals, less than about 0.06 ppm of any metals, less than compounds, organophosphates, organophosphites, organo
about 0.05 ppm of any metals, less than about 0.04 ppm of phosphonates, orthophosphoric acid, metaphosphoric acid,
any metals, less than about 0.03 ppm of any metals, less than pyrophosphoric acid, tripolyphosphoric acid, phosphorous
about 0.02 ppm of any metals, or less than about 0.01 ppm 10
acid, hypophosphorous acid, bismuth phosphate, monoam
of any metals. monium phosphate, diammonium phosphate, monammo
In some embodiments, the starting materials for use in the nium phosphite; salts of phosphoric acid esters having at
production of new polymers obtained from depolymerizing
polyethylene terephthalate contains trace amount of cata least one free alcoholic hydroxyl group, Sodium betaglyc
lysts, inhibitors, or stabilizers. In some embodiments, the 15 erophosphate, calcium betaglycerophosphate, phosphotung
catalysts, inhibitors, or stabilizers were present in the start stic acid, ammonium phosphotungState, sodium phospho
ing polyethylene terephthalate Inhibitors work by interfering tungstate, tertiary phosphines, tripropylphosphine,
with the chain initiation and/or chain propagation steps of triphenylphosphine, ethylphenyltolylphosphine, quaternary
the polymerization during manufacture and purification phosphonium compounds, triphenylmethylphosphonium
when the monomers are at elevated temperatures. Stabilizers iodide, triphenylbenzylphosphonium chloride, and quater
are used in the polymerization process to sequester the nary phosphonium compounds.
catalysts in an attempt to reduce the degradation and dis In some embodiments, the process is as follow:
coloration of the polymer comprising an ester functionality. Polyethylene terephthalate is introduced into a reactor. In
The polymerization catalysts would eventually begin to Some embodiments, the reactor is made out of an inert
catalyze or encourage the degradation of the polymer 25 material. In some embodiments, the reactor is made out of
formed in the condensation reaction. For example, degra stainless steel. In some embodiments, the reactor is made out
dation of polyethylene terephthalate results in the formation of high density polyethylene (HDPE).
of acetaldehyde and the discoloration or yellowing of poly In some embodiments, polyethylene terephthalate is
ethylene terephthalate. mixed in with debris, such as, but not limited to bottle cap,
In some embodiments, the catalyst comprises at least one 30 glue, paper, residual liquid, dirt, or a combination thereof.
of germanium compounds, titanium compounds, antimony In some embodiments, polyethylene terephthalate is
compounds, Zinc compounds, cadmium compounds, man mixed in with other polymers, such as, but not limited to,
ganese compounds, magnesium compounds, cobalt com polyethylene, high density polyethylene, low density poly
pounds, silicon compounds, tin compounds, lead com ethylene, polypropylene, or a combination thereof.
pounds, and aluminum compounds. 35 A non-polar solvent is added to the polyethylene
In some embodiments, the catalyst comprises at least one terephthalate followed by an agent capable of breaking the
of germanium dioxide, cobalt acetate, titanium tetrachloride, ester functionality.
titanium phosphate, titanium tetrabutoxide, titanium tetrai In some embodiments, the agent is a mixture of a base and
Sopropoxide, titanium tetra-n-propoxide, titanium tetra an alcohol. In some embodiments, the agent is a mixture of
ethoxide, titanium tetramethoxide, a tetrakis(acetylacetona 40 an acid and an alcohol. In some embodiments, the non-polar
to) titanium complex, a tetrakis(2.4-hexanedionato)titanium Solvent and the agent are added simultaneously. In some
complex, a tetrakis(3.5-heptanedionato)titanium complex, a embodiments, the agent is added prior to the non-polar
dimethoxybis(acetylacetonato)titanium complex, a Solvent. In some embodiments, the agent is added after the
diethoxybis(acetylacetonato)titanium complex, a diiso addition of the non polar solvent.
propoxybis(acetylacetonato)titanium complex, a di-n- 45 Upon addition of the agent capable of breaking the ester
propoxybis(acetylacetonato)titanium complex, a dibutoxy functionality, the depolymerization of the polyethylene
bis(acetylacetonato)titanium complex, titanium terephthalate starts.
dihydroxybisglycolate, titanium dihydroxybislactate, tita In some embodiments, the reaction is run at atmospheric
nium dihydroxybis(2-hydroxypropionate), titanium lactate, pressure.
titanium octanediolate, titanium dimethoxybistriethanol 50 In some embodiments, the reaction is run at ambient
aminate, titanium diethoxybistriethanol aminate, titanium temperature.
dibutoxybistriethanol aminate, hexamethyl dititanate, hexa In some embodiments, the reaction is exothermic. In some
ethyl dititanate, hexapropyl dititanate, hexabutyl dititanate, embodiments, the reaction is exothermic and the tempera
hexaphenyldititanate, octamethyl trititanate, octaethyl triti ture of the reaction mixture rises to at least 30° C., at least
tanate, octapropyl trititanate, octabutyl trititanate, octaphe 55 35° C., at least 40°C., at least 45° C., at least 50° C., at least
nyl trititanate, a hexaalkoxy dititanate, Zinc acetate, manga 55° C., or even at least 60° C. However, no external heat
nese acetate, methyl silicate, Zinc chloride, lead acetate, Sources are used to increase the temperature of the reaction
Sodium carbonate, sodium bicarbonate, acetic acid, sodium mixture.
Sulfate, potassium sulfate, Zeolites, lithium chloride, mag In some embodiments, the reaction mixture is stirred. In
nesium chloride, ferric chloride, Zinc oxide, magnesium 60 Some embodiments, the reaction mixture is not stirred.
oxide, calcium oxide, barium oxide, antimony trioxide, and In some embodiments, after completion of the depolymer
antimony triacetate. ization reaction, a Solid containing terephthalic acid,
In some embodiments, the inhibitor comprises at least one terephthalic acid salts, terephthalic acid derivatives, unre
of nitrobenzene, butylated hydroxyl toluene (BHT), buty acted polymers, and debris is obtained. In some embodi
lated hydroxyanisole (BHA), diphenyl picryl hydrazyl 65 ments, the terephthalic acid derivatives are terephthalic
(DPPH), tertiary-butyl catechol (TBC), hydroquinone, or a acid/ethylene glycol oligomers, terephthalic acid ester, or a
combination thereof. combination thereof. In some embodiments, the terephthalic
US 9,550,713 B1
17 18
acid derivatives are dimethyl terephthalate, 4-(methoxycar embodiments, the precipitate obtained is about 99.4% pure
bonyl)benzoic acid, or a combination thereof. terephthalic acid. In some embodiments, the precipitate
In some embodiments, the solids contain a major amount obtained is about 99.3% pure terephthalic acid. In some
of terephthalic acid salts, a minor amount of terephthalic embodiments, the precipitate obtained is about 99.2% pure
acid derivatives, unreacted polymers, and debris. terephthalic acid. In some embodiments, the precipitate
In some embodiments, the solids contain a minor amount obtained is about 99.1% pure terephthalic acid. In some
of terephthalic acid salts, a major amount of terephthalic embodiments, the precipitate obtained is about 99.0% pure
acid derivatives, unreacted polymers, and debris. terephthalic acid. In some embodiments, the precipitate
In some embodiments, the solids do not contain any obtained is about 98.9% pure terephthalic acid. In some
terephthalic acid salts but only terephthalic acid derivatives, 10 embodiments, the precipitate obtained is about 98.8% pure
unreacted polymers, and debris. In some embodiments, the terephthalic acid. In some embodiments, the precipitate
terephthalic acid derivatives comprise 4-(methoxycarbonyl) obtained is about 98.7% pure terephthalic acid. In some
benzoic acid. embodiments, the precipitate obtained is about 98.6% pure
In some embodiments, the reaction mixture is filtered to terephthalic acid. In some embodiments, the precipitate
obtain a filter cake and a filtrate. In some embodiments, the 15 obtained is about 98.5% pure terephthalic acid. In some
reaction mixture is centrifuged to separate the Solids from embodiments, the precipitate obtained is about 98.4% pure
the liquids. In some embodiments, the reaction mixture is terephthalic acid. In some embodiments, the precipitate
purified by liquid/liquid extraction. obtained is about 98.3% pure terephthalic acid. In some
In some embodiments, the filter cake obtained is washed embodiments, the precipitate obtained is about 98.2% pure
with some additional alcohol. In some embodiments, the terephthalic acid. In some embodiments, the precipitate
filter cake obtained is washed with some deionized water. obtained is about 98.1% pure terephthalic acid. In some
In some embodiments, the filter cake contains a major embodiments, the precipitate obtained is about 98.0% pure
amount of 4-(methoxycarbonyl)benzoic acid. In some terephthalic acid.
embodiments, 4-(methoxycarbonyl)benzoic acid is isolated The filtrate comprising the alcohol solvent and non polar
and purified. 25 Solvent is collected in a container.
In some embodiments, the filter cake obtained is added to In some embodiments, the filtrate comprises at least one
an aqueous basic Solution. In some embodiments, the filter of ethylene glycol, ethylene glycol derivatives, the alcoholic
cake comprises terephthalic acid derivatives. In some solvent, solubilized terephthatic acid, and soluble impurities.
embodiments, the terephthalic acid derivatives comprise at In some embodiments, the Soluble impurities are catalysts,
least one of terephthalic acid/ethylene glycol oligomers, 30 inhibitors, stabilizers, pigments, or residual food that were
terephthalic acid mono esters, and terephthalic acid diesters. present in the starting polyethylene terephthalate.
In some embodiments, the terephthalic acid derivatives are The filtrate is distilled. In some embodiments, the distil
converted to terephthalic acid upon contact with the basic lation is done at atmospheric pressure (about 14 psi) or under
solution. The solution is then filtered to remove non soluble pressure (up to about 0.4 psi). In some embodiments, the
unreacted polymers, non Soluble oligomers, and debris. The 35 distillation is performed with increased temperature. In
filtrate obtained contains the solubilized terephthalic acid Some embodiments, the distillation temperature is less than
salts. The pH of the filtrate obtained (either directly or about 100°C. In some embodiments, the distillate comprises
following the basic treatment) is then lowered. In some the non polar solvent, the alcohol solvent, traces ethylene
embodiments, the pH is lowered by addition of an aqueous glycol, traces water, and traces ethylene glycol derivatives.
acid. In some embodiments, the pH is lowered by addition 40 In some embodiments, the distillate comprising the non
of dry ice. In some embodiments the pH is lowered to 9. In polar solvent and the alcohol solvent is reused in the first
some embodiments the pH is lowered to 8.5. In some step of the depolymerization process of the present inven
embodiments the pH is lowered to 8. In some embodiments tion. In some embodiments, additional amounts of non-polar
the pH is lowered to 7.5. In some embodiments the pH is solvent and alcohol solvent are added.
lowered to 7. In some embodiments the pH is lowered to 6.5. 45 In some embodiments, the residue remaining after the
In some embodiments the pH is lowered to 6. In some distillation comprises ethylene glycol, ethylene glycol
embodiments the pH is lowered to 5.5. In some embodi derivatives, and non-volatile impurities. In some embodi
ments the pH is lowered to 5. In some embodiments the pH ments, the non-volatile impurities are solids. In some
is lowered to 4.5. In some embodiments the pH is lowered embodiments, the non-volatile impurities are filtered off.
to 4. In some embodiments the pH is lowered to 3.5. In some 50 The filtrate comprises ethylene glycol and ethylene glycol
embodiments the pH is lowered to 3. In some embodiments derivatives.
the pH is lowered to 2.5. In some embodiments the pH is In some embodiments, the ethylene glycol is purified by
lowered to 2. In some embodiments the pH is lowered to 1.5. distillation. In some embodiments, the distillation is done at
In some embodiments the pH is lowered to 1. atmospheric pressure (about 14 psi) or under pressure (up to
The precipitate is filtered. In some embodiments, the 55 about 0.4 psi). In some embodiments, the distillation is
precipitate is washed with Some additional alcohol. In some performed with increased temperature. In some embodi
embodiments, the precipitate is washed with Some deionized ments, the distillation temperature is less than about 250° C.
water. The precipitate is then dried. In some embodiments, the ethylene glycol is purified by
In some embodiments, the precipitate obtained is pure ceramic membrane filtration.
terephthalic acid. In some embodiments, the precipitate 60 In some embodiments, the ethylene glycol is about 99.9%
obtained is about 99.9% pure terephthalic acid. In some pure. In some embodiments, the ethylene glycol is about
embodiments, the precipitate obtained is about 99.8% pure 99.8% pure. In some embodiments, the ethylene glycol is
terephthalic acid. In some embodiments, the precipitate about 99.7% pure. In some embodiments, the ethylene
obtained is about 99.7% pure terephthalic acid. In some glycol is about 99.6% pure. In some embodiments, the
embodiments, the precipitate obtained is about 99.6% pure 65 ethylene glycol is about 99.5% pure. In some embodiments,
terephthalic acid. In some embodiments, the precipitate the ethylene glycol is about 99.4% pure. In some embodi
obtained is about 99.5% pure terephthalic acid. In some ments, the ethylene glycol is about 99.3% pure. In some
US 9,550,713 B1
19 20
embodiments, the ethylene glycol is about 99.2% pure. In embodiments, ambient temperature is 25° C. In some
some embodiments, the ethylene glycol is about 99.1% pure. embodiments, ambient temperature is 26° C. In some
In some embodiments, the ethylene glycol is about 99.0% embodiments, ambient temperature is 27° C. In some
pure. In some embodiments, the ethylene glycol is about embodiments, ambient temperature is 28° C. In some
98.9% pure. In some embodiments, the ethylene glycol is embodiments, ambient temperature is 29° C. In some
about 98.8% pure. In some embodiments, the ethylene embodiments, ambient temperature is 30° C. In some
glycol is about 98.7% pure. In some embodiments, the embodiments, ambient temperature is 31° C. In some
ethylene glycol is about 98.6% pure. In some embodiments, embodiments, ambient temperature is 32° C.
the ethylene glycol is about 98.5% pure. In some embodi As used in this specification and the appended claims,
ments, the ethylene glycol is about 98.4% pure. In some 10
depolymerization, refer to a way of breaking down a poly
mer to its starting material. It is essentially the opposite of
embodiments, the ethylene glycol is about 98.3% pure. In polymerization. In some embodiments, the depolymeriza
some embodiments, the ethylene glycol is about 98.2% pure. tion is achieved by glycolysis, methanolysis or hydrolysis,
In some embodiments, the ethylene glycol is about 98.1% categorized by the depolymerization reactant used, such as
pure. In some embodiments, the ethylene glycol is about glycol, methanol or water, respectively.
98.0% pure. 15
Definition of standard chemistry terms may be found in
reference works, including but not limited to, Carey and
Certain Terminology Sundberg “Advanced Organic Chemistry 4' Ed.” Vols. A
(2000) and B (2001), Plenum Press, New York.
The section headings used herein are for organizational The terms below, as used herein, have the following
purposes only and are not to be construed as limiting the meanings, unless indicated otherwise:
subject matter described. “Linear alkyl refers to a straight hydrocarbon chain
Unless defined otherwise, all technical and scientific radical which is attached to the rest of the molecule by a
terms used herein have the same meaning as is commonly single bond. A linear alkyl comprising up to 4 carbon atoms
understood to which the claimed subject matter belongs. In is referred to as a linear C-C alkyl, likewise, for example,
the event that there are a plurality of definitions for terms 25 a linear alkyl comprising up to 3 carbon atoms is a linear
herein, those in this section prevail. C-C alkyl. Linear alkyl groups include linear C-C alkyl,
It is to be understood that the general description and the linear C-C alkyl, linear C-C alkyl, linear C-C alkyl and
detailed description are exemplary and explanatory only and linear C-C alkyl. Representative alkyl groups include,
are not restrictive of any subject matter claimed. In this methyl, ethyl, propyl, and butyl.
application, the use of the singular includes the plural unless 30 “Branched alkyl refers to a branched hydrocarbon chain
specifically stated otherwise. It must be noted that, as used radical which is attached to the rest of the molecule by a
in the specification and the appended claims, the singular single bond. A branched alkyl comprising between 3 and 4
carbon atoms is referred to as a branched C-C alkyl.
forms “a,” “an and “the include plural referents unless the Representative branched alkyl groups include, but are not
context clearly dictates otherwise. In this application, the use limited to t-butyl, S-butyl, i-butyl, i-propyl, and S-propyl.
of “or” means “and/or unless stated otherwise. Further 35 “Cyclic alkyl refers to a cyclic hydrocarbon chain radical
more, use of the term “including as well as other forms, which is attached to the rest of the molecule by a single
such as “include”, “includes,” and “included,” is not limit bond. A cyclic alkyl comprising between 3 and 8 carbon
ing. atoms is referred to as a cyclic C-C alkyl. Cyclic alkyl
Unless the context requires otherwise, throughout the groups include cyclic C-C alkyl, cyclic C-C, alkyl, cyclic
specification and claims which follow, the word “comprise' 40 C-C alkyl, and cyclic C-C alkyl. Representative cyclic
and variations thereof. Such as, "comprises and "compris alkyl groups include, but are not limited to cyclopropyl.
ing” are to be construed in an open, inclusive sense, that is, cyclobutyl, cyclopentyl, cyclohexyl, or cycloheptyl.
as “including, but not limited to.” Further, headings pro “Linear C-C alcohol”, “branched C-C alcohol', and
vided herein are for convenience only and do not interpret “cyclic C-C alcohol refer to the formula ROH where R is
the scope or meaning of the claimed invention. 45 an alkyl radical as defined above. Representative alcohol
As used in this specification and the appended claims, the includes, but are not limited to, methanol, ethanol, n-pro
singular forms “a,” “an, and “the include plural referents panol, n-butanol, t-butanol, S-butanol, i-butanol, i-propanol,
S-propanol, cyclopropanol, cyclobutanol, cyclopentanol,
unless the content clearly dictates otherwise. It should also cyclohexanol, or cycloheptanol. In some embodiments, the
be noted that the term 'or' is generally employed in its sense alcohol is methanol. In some embodiments, the alcohol is
including “and/or unless the content clearly dictates other 50
ethanol.
wise.
As used herein, the term “about' or “approximately "C-C Alkoxy' refers to a radical of the formula —OR
where R is an alkyl radical as defined having from one to
means within 20%, preferably within 10%, and more pref four carbon atoms. Representative alkoxy groups include,
erably within 5% of a given value or range. but are not limited to, methoxy, ethoxy, n-propoxy, n-butoxy,
As used herein, ambient temperature is a colloquial 55 t-butoxy, S-butoxy, i-butoxy, i-propoxy, and S-propoxy. In
expression for the typical or preferred indoor (climate Some embodiments, the alkoxy is methoxy. In some embodi
controlled) temperature to which people are generally accus ments, the alkoxy is ethoxy.
tomed. It represents the Small range oftemperatures at which
the air feels neither hot nor cold, approximately 21°C. In EXAMPLES
some embodiments, ambient temperature is 25+5° C. In 60
some embodiments, ambient temperature is 18°C. In some The following examples are intended to illustrate but not
embodiments, ambient temperature is 19° C. In some limit the disclosed embodiments.
embodiments, ambient temperature is 20° C. In some
embodiments, ambient temperature is 21° C. In some Example 1
embodiments, ambient temperature is 22° C. In some 65
embodiments, ambient temperature is 23° C. In some Washed and shredded polyethylene terephthalate (2 Kg,
embodiments, ambient temperature is 24° C. In some including caps and labels) was introduced in a stainless steel
US 9,550,713 B1
21 22
reactor. Dichloromethane (300 mL) was added and the TABLE 1.
mixture was stirred at ambient temperature and atmospheric
Properties Results Units Method
pressure. Potassium hydroxide (716 g) dissolved in metha
nol (6 L) followed by an additional amount of methanol (0.4 4-Carboxyben- 14.4 l HPLC-MS
L) were then added to the reaction mixture and the resulting Zaldehyde
para-Toluic Acid
944 l HPLC-MS
mixture was stirred for 66 minutes (aliquots taken at 2, 10, Al O.345 O.OO)4 l CP-MS
25, 35, and 50 minutes showed that the depolymerization As under detection l CP-MS
reaction was complete after 25 minutes). The reaction mix Ca
limit
4.591 O.O21 l CP-MS
ture was then filtered. The filter cake (containing caps, 10 Co O.OO7 O.O22 l CP-MS
labels, non depolymerized polyethylene terephthalate, trace Cr O.235 O.OO7 l CP-MS
ethylene glycol, and Small amount of the potassium salt of Fe O-360 O.OO8 l CP-MS
terephthalic acid) was washed with deionized water. K
Mn
180 - 2592
O.O14 O.OO6
l
l
CP-MS
CP-MS
The pH of the filtrate was lowered to about 2 by addition Mo O.OO9 O.OO1 l CP-MS
of aqueous Sulfuric acid. The precipitate obtained was 15 Na 126.362 - 1364 l CP-MS
filtered and washed with a minimum amount of methanol to N O.O19 O.OO1 l CP-MS
yield terephthalic acid. T O.O29 O.OO1 l CP-MS
The filtrate was distilled to first recover the dichlorometh Pb O.146 O.OO2 l CP-MS

ane and the methanol and then to recover the ethylene


glycol.
Example 5
Example 2
In a 250 mL pyrex flask was introduced polyethylene
Comparative Example terephthalate (10 g) and dichloromethane (6 g). Separately
Experiment #1 25 sodium hydroxide (4.32 g) was dissolved in water (3.6 g)
and methanol (32.93 g). After 20 min., the basic solution was
added to the dichloromethane/PET mixture and the admix
Washed and shredded polyethylene terephthalate (2.5 g. ing was continued for 10 days at room temperature and
including caps and labels) was added to a solution of atmospheric pressure. Water (200 mL) was added to dissolve
potassium hydroxide (10 mL, 5M in methanol) and DMSO
(40 mL). The resulting mixture was stirred at ambient all the terephthalic acid salts and the solution was filtered to
temperature and atmospheric pressure for 30 minutes. yield 0.1 g of unreacted starting material or insoluble
oligomers. The aqueous solution was acidified and a pre
Experiment #2 cipitate formed. The solids were filtered to yield 99% of
terephthalic acid and terephthalic acid derivatives.
Washed and shredded polyethylene terephthalate (2.5 g. 35
Example 6
including caps and labels) was added to a solution of
potassium hydroxide (10 mL, 5M in methanol) and dichlo In a 250 mL pyrex flask was introduced polyethylene
romethane (40 mL). The resulting mixture was stirred at terephthalate (10 g) and dichloromethane (5 g). Separately
ambient temperature and atmospheric pressure for 30 min Sodium hydroxide (2.65 g) and potassium hydroxide (1.5 g)
utes. 40
After 30 minutes complete depolymerization was were each dissolved in methanol (50 g). After 20 min., the
basic solutions were added to the dichloromethane/PET
achieved in Experiment #2 while the depolymerization in
Experiment #1 had barely started. After three days the mixture and the admixing was continued for 3 days at room
depolymerization in the Experiment #1 was still not com temperature and atmospheric pressure. Water (200 mL) was
plete. 45 added to dissolve all the terephthalic acid salts and
In the case of Experiment #2, 1.7 g of terephthalic acid terephthalic acid derivatives. The solution was filtered to
was recovered. yield 0.85 g of unreacted starting material or insoluble
oligomers. The aqueous solution was acidified and a pre
Example 3 cipitate formed. The solids were filtered to yield 4.65 g of a
50 mixture of terephthalic acic/4-(methoxycarbonyl)benzoic
Washed and shredded polyethylene terephthalate (58 g. acid (2.16:1 ratio).
including caps and labels) was added to a solution of
potassium hydroxide (100 g in methanol) and dichlorometh What is claimed is:
ane. The resulting mixture was stirred at atmospheric pres 1. A process for depolymerizing a polymer comprising an
sure to yield 40 g of terephthalic acid. 55 ester functionality to the corresponding alcohol and carbox
ylic acid components for use in the production of new
Example 4 polymers, comprising admixing the polymer with a mixture
of:
Dichloromethane (4.5 Kg) was added to washed and (i) a non-polar solvent for Swelling the polymer; and
shredded white polyethylene terephthalate without caps or 60 (ii) an agent for breaking the ester functionality consisting
labels (BLT grade, 15 Kg). The mixture was stirred at of a mixture of an alcohol and a hydroxide;
ambient temperature for 18 minutes followed by addition of wherein the admixing is continued for a sufficient time to
a mixture of potassium hydroxide (8.8 Kg) in methanol (30 depolymerize at least a portion of the polymer to the
Kg). The internal temperature was measured to be 50° C. corresponding alcohol and carboxylic acid compo
The resulting mixture was stirred for 45 minutes. The 65 nents; and
impurity profile of the resulting terephthalic acid is shown in wherein the process is performed without applying exter
table 1. nal heat.
US 9,550,713 B1
23 24
2. The process of claim 1, wherein the mixture of the 15. A process for depolymerizing of polymer comprising
alcohol and the hydroxide is added to the polymer simulta an ester functionality to the corresponding alcohol and
neously with the non-polar solvent. carboxylic acid components for use in the production of new
3. The process of claim 1, wherein the ratio of the polymers, comprising admixing the polymer with a mixture
of:
non-polar solvent to alcohol is about 1:10 to about 1:50 about 3 to about 5% (vol.) of a non-polar solvent for
(v:v). Swelling the polymer, wherein the non-polar solvent is
4. The process of claim 1, wherein the polymer is admixed a halogenated solvent;
with the non-polar solvent, the hydroxide, and the alcohol (ii) about 95 to about 97% (vol.) of a linear C-C alcohol:
for about 0 h to about 5 h. and
10
5. The process of claim 4, wherein the polymer is admixed (iii) a hydroxide:
with the non-polar solvent, the hydroxide, and the alcohol at wherein the admixing is continued for about 1 h; and
atmospheric pressure. wherein the process is performed without applying exter
6. The process of claim 1, wherein the non-polar solvent nal heat.
for swelling the polymer is a halogenated solvent. 16. The process of claim 15, wherein the polymer com
7. The process of claim 1, wherein the alcohol is a linear
15 prising the ester functionality is polyethylene terephthalate
C-C alcohol. and wherein the corresponding alcohol and carboxylic acid
8. The process of claim 1, wherein the hydroxide is components for use in the production of new polymers are
Selected from a group consisting of an alkali metal hydrox terephthalic acid or salt thereof and ethylene glycol.
ide, an alkaline earth metal hydroxide, an ammonium 17. The process of claim 16, wherein the terephthalic acid
hydroxide, and a combination thereof. or salt thereof obtained from the depolymerization process
9. The process of claim 1, wherein the polymer is in the contains less than about 1% impurity (w/w).
form of waste material. 18. The process of claim 17, wherein the impurity com
10. The process of claim 9, wherein the waste material prises at least one of isophthalic acid, phthalic acid, 4-meth
further comprises debris that do not include polymers com ylbenzoic acid, 4-formylbenzoic acid, and metals.
prising an ester functionality.
25 19. A process for depolymerizing polyethylene terephtha
11. The process of claim 10, wherein debris comprises at late to terephthalic acid or salt thereof and ethylene glycol
least one of bottle caps, glue, paper, residual liquid, and dirt. comprising admixing polyethylene terephthalate with a mix
ture of:
12. The process of claim 1, wherein the polymer com (i) about 3 to about 5% (vol.) of a non-polar solvent for
prising the ester functionality is polyethylene terephthalate 30
Swelling the polymer, wherein the non-polar solvent is
and wherein the corresponding alcohol and carboxylic acid a halogenated solvent;
components for use in the production of new polymers are
terephthalic acid or salt thereof and ethylene glycol. (ii) about 95 to about 97% (vol.) of a linear C-C alcohol:
and
13. The process of claim 12, wherein the terephthalic acid (iii) a hydroxide:
or salt thereof obtained from the depolymerization process 35
wherein the admixing is continued for about 1 h; and
contains less than about 1% impurity (w/w). wherein the process is performed without applying exter
14. The process of claim 13, wherein the impurity com nal heat.
prises at least one of isophthalic acid, phthalic acid, 4-meth
ylbenzoic acid, 4-formylbenzoic acid, and metals. CE: ck ci: ck i: