United States Patent [19] [111 3,884,850

Ostrowski [45] May 20, 1975

[54] CONTINUOUS ATMOSPHERIC 3,344,091 9/1967 Russin et a1. ...................... .. 260/2.3

DEPOLYMER‘ZATION OF POLYESTER 3,506,622 4/1970 Higgins .............................. .. 260/2.3
[75] Inventor: Henry S. Ostrowski, 3729 Country OTHER PUBLICATIONS
Ridge Rd., Charlotte, N.C. 28211
Etienne et al., Def. Pub. of Ser. No. 784,483, ?led
[73] Assignee: Fiber Industries, Inc., Charlotte, Dec. 17, 1968, published in 869 0.6. 1385, on
N.C. 12/30/69, Def. Pub. No. T869,017.
[22] Filed: Feb. 13, 1970
[21] Appl. No.: 11,221 Primary Examiner—Lorraine A. Weinberger
Assistant Examiner-E. Jane Skelly
[52] US. Cl ......... .. 260/2.3; 260/468 R; 260/473 R;
260/475 D; 260/485 G [57] ABSTRACT
[51] Int. Cl. .......................................... .. C07c 69/82
Process for the depolymerization of high molecular
[581 Field of Search ........................ .. 260/475 D, 2.3
weight, i.e., ?ber-formable, polyesters to low molecu
lar weight oligomer depolymerizate in a continuous
[56] References Cited process at atmospheric pressure.
UNITED STATES PATENTS
2,727,882 12/1955 Vodonik ........................ .. 260/475 P 9 Claims, 3 Drawing Figures
PATENTED MAY 2 0 i975 , 8 8 4, 85 O
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INVENTOR
FIGURE 1 HENRY S. OSTROWSKI

BY ,gujgmaa
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ATTORNEY
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CHAIN LENGTH

THEORETICAL AMOUNT OF GLYCOL NEEDED TO

DEPOLYMERIZE POLYETHYLENE TEREPHALATE
TO A GIVEN CHAIN LENGTH

INVENTOR
2 HENRY S OSTR‘OWSKI

BY my.
ATTORNEY.
9,1;(9475524AY20B75 ' 3, 884,850 ,

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CHAIN LENGTH

POLY’ETHYLENE TEREPHALATE MELTING POINT

AS A FUNCTION OF CHAIN LENGTH

'INVENTOR
3 ‘HENRY S. OSTROWSKI .

BY 6W”
ATTORNEY
 3,884,850
1 2
CONTINUOUS ATMOSPHERIC reaction side products such as polyglycol ethers, to
DEPOLYMERIZATION OF POLYESTER form a feed material for polycondensing that can be
subsequently formed into ?lms and ?bers of excellent
BACKGROUND OF THE INVENTION properties. Although the present invention is later de
This invention relates to polymerization processes 5 scribed with particular reference to a continuous poly
and, more particularly, to improvements in the contin ethylene terephthalate direct esteri?cation
uous production of polymethylene terephthalate poly polycondensation process, it is of course understood
mers of dicarboxylic acids and dihydric alcohols that the principles described herein are equally applica
wherein waste and scrap polyester material is depolym ble to scrap polymer produced from ester interchange
erized to low molecular weight oligomer depolymeri monomers as well as numerous other polyesters of dif
zate in a continuous depolymerization process to be fed ferent monomer content as described in greater detail
directly into batch or continuous polyester polymeriza hereinafter.
tion operations without deleteriously affecting polyes For economic reasons it is in many instances desir
ter polymer properties. Even more speci?cally, the able to return polyester scrap material directly to the
present invention concerns a continuous process for 15 polymerization system. For a variety of reasons large
the depolymerization of ?ber and ?lm-forming polyeth quantities of polyester waste are accumulated during
ylene terephthalate scrap material, utilizing atmo polyester production, extrusion and post-extrusion pro
spheric pressure conditions, to a low molecular weight cessing, i.e., reject polyester, broken ?laments, trim
polyethylene terephthalate oligomer mixture which and the like. However, when high molecular weight
may be employed directly as feed material, i.e., 100 20 solid polyester is fed as such along with virgin monomer
percent depolymerizate or 5 to 100 percent by weight to the polymerization reactor, numerous disadvantages
depolymerizate, in polymerization procedures for pro are present, most notably of which are color formation,
ducing polyethylene terephthalate of high intrinsic vis production of undesirable side products which lower
cosity, for example, above 0.4 and where desired 0.8 to product melting temperature, inhibition of polymeriza
l .5. The resulting polyethylene terephthalate is charac 25 tion which lowers ?nal product viscosity and clogging
terized by molecular weight, color and other properties ‘ of ?ow lines due to plugging with undissolved polymer.
such as percent purity required for production of Because of these dif?culties and the inferior character
shaped articles such as ?bers and ?lms, comparable to istics of the ?nal product, considerable effort has been
those of polymer prepared from 100 percent virgin expanded to develop commercially feasible procedures
monomer under essentially identical process condi 30 to rapidly depolymerize polyesters of high intrinsic vis
tions. cosity to low molecular weight monomer of sufficient
Commercial, melt phase, production of polyethylene purity to enable direct incorporation into the polymer
terephthalate suitable for conversion into strong and ization system without’ deleteriously affecting ?nal
durable shaped articles such as ?bers or ?lms usually
involves either an ester-interchange or direct esteri?
polymer properties. Prior art depolymerization and
cation route for preparation of terephthalate monomer
similar polyester decomposition techniques have been
which is subsequently polymerized into extrudable found objectionable in many respects when tried com
polymer of suf?cient intrinsic viscosity by multi-step mercially during continuous operations. The primary
polycondensation processes. (Athough the feed for po drawbacks with respect to the art are, for example, the
lymerization or polycondensation is termed in the ‘art’ 40 necessity of using various additives involving uneco
monomer, the feed material is actually a mixture of 1
nomical procedures and producing physical changes in
true monomer, i.e., bis(hydroxyethyl) terephthalate or the ?nal product of polymerization. As examples of the
BHET, and low molecular weight oligomers containing additive type technique, there may be mentioned the
up to about 5 to 15 repeating units based on tereph addition of a strong acid to precipitate terephthalic
45 acid from a scrap-ethylene glycol system for re
thalic acid in the case of polyethylene terephthalate.)
In the ester-interchange reaction, a readily available esterification and the employment of ethylene oxide
or producible dialkyl dicarboxylate, i.e., dimethyl tere with molten scrap for monomer regneration purposes.
phthalate, is reacted under ester-interchange condi Other processes of the prior art necessitate the incon
tions with the necessary glycol, i.e., ethylene glycol, to venience associated with multi-step depolymerization,
produce the desired monomeric ester, BHET in the pressure requirements and batch operations. For in
case of ethylene glycol and dimethyl terephthalate or stance, U.S. Pat. No. 3,257,335 to Whit?eld, Jr. et. al.
as discussed hereinbefore a low molecular weight oligo discloses a two-step depolymerization process where
mer mixture for subsequent polycondensation. Obvi monomer must be continuously recycled to a dissolver
ously, the ester-interchange method is not the most di containing scrap to accomplish partial depolymer
rect procedure for producing monomer since a dialkyl ization prior to a second depolymerization operation
ester must ?rst be obtained prior to conversion to the under superatomospheric pressure, and US. Pat. No.
glycol ester. Recently, there has been disclosed in the 3,344,091 to Russin et al. disclosing a batch operation
patent and literature art processes by which tereph utilizing the addition of a dialkyl ester to a mixture of
thalic acid can be rapidly esteri?ed by direct reaction glycol and scrap. Since Russin et al. state that their pro
with a glycol, i.e., ethylene glycol, 1,4-butanediol and cess is also operable in the absence of dialkyl ester, it
the like, utilizing superatomospheric pressure condi is apparent that autogenicpressure is developed within
tions and temperatures above the boiling point of the his system. Ethylene glycol alone cannot dissolve sig
glycol in closed-system operations. In this regard, see ni?catn quantities of high molecular weight polyethyl-‘
Munro and Maclean US. Pat. No. 3,050,533. Pressure 65 ene terephthalate below the melting point thereof
conditions appear to enable the attainment of a suffi under atmospheric pressure conditions, an applied or
ciently high percent esteri?cation in the direct reaction autogenic pressure of about 50 p.s.i.g. being required. I
sequence, without formation of signi?cant amounts of Russin’s temperature of polymerization is well below
 3,884,850
3 4
the melting temperature of polyethylene terephthalate formable quality i.e., 0.4 to 1.5 intrinsic viscosity can
polymer. be continuously depolymerized at atmospheric pres
Therefore, it is an object of the present invention to sure with as little as 10 to 15 percent ethylene glycol
provide a process for the depolymerization of high mo boiloff (boiling point of about 197°C) in the presence
lecular weight polyesters. More specifically, it is an ob of about a 10 to 15 percent stoichiometric excess of
ject of the present invention to provide a process for glycol at a temperature above about 220°C, and pref
continuously depolymerizing scrap polyester of high erably below 250°C, to produce monomer'or, more
intrinsic viscosity at atomospheric pressure in a single precisely, an oligomer mixture of average chain length
step operation to low molecular weight oligomer mix of about three monomer units based on terephthalic
ture depolymerizate which can be directly fed into a acid and melting at about 200°C. which can be fed into
polymerization system without deleteriously affecting a polyester polycondensation system, i.e., ‘low’ poly
polymer properties. merizer, with or without virgin monomer to produce
Another object of the invention is to provide a polymer of excellent quality.
method for the continuous depolymerization of poly In another preferred embodiment of the invention, as
ethylene terephthalate which does not require multi I5 disclosed in greater detail hereinafter, polytetrameth
step operations or applied pressures. Still another ob ylene terephthalate is depolymerized to low molecular
ject of the invention is to provide a process operating weight monomer.
at atmospheric pressure for the depolymerization of DETAILED DESCRIPTION
high molecular weight polyesters of a dicarboxylic acid
and a dihydric alcohol to the corresponding low molec 20 A better understanding of the invention may be ob
ular Weight esters by the addition of approximately stoi tained from the drawing wherein: , .
chiometric amounts of glycol and scrap following an FIG. 1 schematically illustrates the continuous depo
initial charge of monomer to the system at tempera lymerization process of the invention, . ,
tures below the melting point of the polymer. FIG. 2 graphically represents the stoichiometric
25 quantity of ethylene glycol required to depolymerize
THE INVENTION polyethylene terephthalate of average intrinsic viscos
In accordance with the present invention, it has now ity within the range of about 0.70-0.90 to a given chain
been found that high molecular weight polyesters pre length and
pared from a dicarboxylic acid and a dihydric alcohol FIG. 3 graphically correlates polyethylene tere
can be depolymerized to a lower molecular weight 30 phthalate melting point with chain length. Referring to
depolymerizate suitable for direct introduction into a FIG. 1, it is seen that particulate polyester is stored in
polymerization system by dissolving said polyester in a storage hopper 1 which contains a vibrating lower
the corresponding monomer and adding thereto a dihy chamber 2 emptying into a vibrating screw feeder 3. As
dric alcohol or functional derivative thereof and main depicted, N2 is forced through the screw feeder under
taining the resultant mixture at a temperature above 35 slight pressure greater than about 0.01 p.s.i.g. to pre
the boiling point of the alcohol under substantially at vent glycol vapors from “blowing back” into the feeder
mospheric pressure conditions until the desired degree and clogging the same. The waste and glycol are fed
of depolymerization has been attained. into the top of an agitated depolymerizer 4 equipped
With respect to a preferred embodiment of the inven with a bottom drain 5 to remove foreign matter without
40 process interruption, a side outlet 6 through which
tion, it has now been found that high molecular weight
polymeric esters of dicarboxylic acids and dihydric al oligomer is passed to a ?rst stage polyester polymer
cohols can be depolymerized to low molecular weight izer, a vertical screen 7 of small enough mesh, i.e., 10
oligomer mixtures by charging to a suitable reaction to 50, to prevent comminuted matter from contaminat
vessel said high polymeric ester, a stoichiometric ex 45 ing the oligomer effluent, and an agitator 8. The oligo
cess of the amount of dihydric alcohol, corresponding mer issuing from the polymerizer, preferably ?ltered,
to the glycol employed in the production of the ester, may be directly added to the ?rst stage polymerizer as
required to depolymerize back to the extent desired a sole feed or admixed with virgin monomer in any de
and an initial charge of solvent selected from the class sired ratio, i.e., 1 to 99 parts. by weight reconstituted
consisting of lower molecular weight esters, oligomers, oligomer and correspondingly 99 to 1 parts by weight
and polyesters of said dicarboxylic acid and said dihy virgin monomer but preferably about 1 to 25 parts
dric alcohol; heating the reaction mixture to a tempera reconstitued oligomer to about 99 to 75 parts virgin
ture above the boiling point of the glycol but below the monomer. The rate of reaction in the depolymerizer is
melting point of the polymer for a time suf?cient to ef so rapid as to nearly eliminate excessive vaporization of
fectuate the desired degree of depolymerization while glycol, only a quantity of glycol about 10 percent in ex
maintaining the system under atmospheric pressure cess fo the stoichiometric amount being required. How
and continuously removing oligomer while continu ever, for the purpose of vapor removal, a conduit 9
ously adding higher molecular weight polyester and leads from the vapor space above the liquid to a spray
glycol to the reaction system. condenser 10 in which a glycol or water spray con
In one aspect of the invention, which may be consid denses vaporous ef?uent which would consist primarily
ered as a more speci?c preferred embodiment thereof, of glycol, small amounts of water and any volatile mat
the polymeric ester is depolymerized back to low mo ter present such as yarn ?nish materials. Indeed, a dis
lecular weight oligomer of melting point slightly in ex tinct advantage of the invention is that most materials
cess of the boiling point of the dihydric alcohol, assur applied to the polymer subsequent to high polymeriza
ing maximum depolymerization with minimal mono 65 tion, i.e., ?lm antistatic coatings, yarn lubricants and
mer boiloff.
the like, will “?ash off" at the temperatures employed
With respect to polyethylene terephthalate, it has for depolymerization eliminating washing steps prior to
been found that reject and scrap material of ?ber depolymerization. The spray condenser can also serve
 3,884,850
5 6
an additional function where employed by creating a from varying amounts of adipic and terephthalic acids
slight vaccum or siphoning effect which also prevents in combination with ethylene glycol, i.e., a copolyester
clogging within the feed lines. containing at least 75 percent terephthalate units. The
A level control device 11 monitors the liquid level in most preferred polyester, polyethylene terephthalate, is
the depolymerizer adjusting the ?ow of scrap from the used to exemplify the invention.
feeder accordingly. Because different densities of scrap The scrap polyester employed in the invention should
will affect the depolymerizer inventory level, one be relatively'free of foreign matter but generally need
should not rely solely upon a measurement of weight not be pre-washed unless it has been converted into ul
addition per unit time as a proper guide for mainte timate product form during which various coatings and
nance of desired depolymerizer volume inventory. The the like have been applied which may not vaporize at
vessel should be agitated, although other means of agi reaction temperatures. Those skilled in the art will be
tation including manipulation of the depolymerizer cognizant of the types of foreign matter which need not
may be employed, to prevent oligomer freezing in lo be removed prior to introduction into the reaction sys
calized areas upon injection of glycol into the system. tem and vice-versa. Conventional yarn ?nishes, of
Rapid dissemination of glycol through out the system course, may “?ash off” during solvation.
is also advantageous because depolymerization occurs Particle shape and size may vary widely depending
nearly simultaneously with the dissolving of scrap in the upon the source, such as spun waste, hard waste such
glycol-oligomer mixture thereby minimizing glycol loss as extrusion ends and chip waste, ?lm, staple tow, and
by vaporization. Once the steady-state reaction is the like. The essential requirement is to assure rapid
reached, utilizing process conditions as described 20 and thorough dissolution of scrap in the glycol
herein, the steady addition of approximately stoichio oligomer mixture. To this end, it is recommended that
metric quantities of scrap and glycol, i.e., about 10 to waste and scrap be segregated according to origin, i.e.,
15 percent excess glycol by weight, correlated with staple ?bers, molded chips, ?lm, etc. and reduced to a
oligomer rate of discharge from the vessel assures a relatively uniform size prior to being fed into the depo
continuous depolymerization reaction at temperatures 25 lymerizer. Various combinations of waste sub-division
above the boiling point of glycol under existing atmo‘ _ according to principles well-known to those skilled in
spheric pressure conditions. the art are applicable, involving the employment of var
The present invention is applicable to polyesters ious machinery such as the guillotine, cutter, granula
formed by the reaction of a dihydric alcohol and a di tor, pelletizer, and the like. As an example, ?ber waste
carboxylic acid or ester-forming derivative thereof fol 30 could be initially passed through a cutter, then granu
lowed by polycondensation as described hereinbefore. lated and ?nally reduced into ?oc of high density by
Suitable glycols are those containing from about two to means of a compactor or pelletizer. Particle shape will
about 10 carbon atoms, preferably two to four carbon be regulated by the speci?c sub-dividing process em
atoms, and as examples thereof there may be men ployed. As a general guideline, but more importantly
tioned'ethylene glycol, propylene glycols such as 1,3 35 because of the rapid rate of reaction coupled with the
propane diol, butylene glycols, such as 1,4-butane diol, known correlation between available surface area and
neopentyl glycol, cycloalkylene-containing compounds rate of dissolution, it is recommended that overall aver
such as tran-bis-l ,4-(hydroxymethyl) cyclohexane, and age particle surface area be below about 0.5 in.2 with
aromatic glycols such as 1,4-bis-(2-hydroxyethyl) ben at least one surface dimension less than 0.25 in.
zene. In general, the diol may contain any suitable or Following comminution, the floc should be continu
ganic moiety between hydroxyl groups but will most ously fed to the depolymerizer in a smooth and steady
often be characterized by methylene radicals attached stream with minimal ?uctuation in rate and‘without
’ to terminal hydroxyl oxygen atoms. Additional exam clogging the feed line. Although various arrangements
ples of suitable glycols will be obvious to those skilled of machinery would suf?ce, it has been found that the
in the art, the term being employed to include diols ca~ particular apparatus arrangement depicted in the draw
pable of supplying the alcoholic moiety of esters form ing consisting of a vibrating bottom discharge bin and
able into fiber-forming polymers. The terms “diol, ” a vibrating screw feeder in which the helix simulta
“dihydric alcohol, ” “glycol” and the like, are used in neously rotates and rapidly reciprocates in an axial, up
terchangeably herein to designate such compounds. 50
and-down motion efficiently and continuously supplies _
The dicarboxylic portion of the ester is a divalent particulate polyester with minimal variation in ?ow
radical which may be aliphatic, aromatic or a combina rate.
tion thereof. Suitable dicarboxylic acids, where the free A consideration of FIGS 2 and 3 illustrates certain of
acid is used to supply the dicarboxylic radical, are the the principles within which the present invention oper
rephthalic acid, maleic acid, adipic acid, azelaic acid, ates. In the case of polyethylene terephthalate, with
isophthalic acid, bibenzoic acid, the various hydroge ethylene glycol boiling at about 197°C, it is readily ap
nated phthalic acids, and the naphthalene dicarboxylic parent that at atmospheric pressure the depolymer
acids, e.g., 1,5-and 2,6-naphthalene dicarboxylic acids, ization reaction can proceed to the dimer-trimer re
e.g., 1,5-and 2,6-naphthalene dicarboxylic acids, 4,4 ' gion, about 2.7 unit average length chain oligomer, at
dicarboxydiphenoxyethane, hydroxycarboxylic acids of which time equilibrium of reaction is reached in the liq
pivalolactone and the like. Of course, copolyesters are uid phase with only a relatively small amount of glycol,
within the scope of the present invention wherein a about 10 to 15, typically about 11.5, percent glycol per
mixture of two or more dicarboxylic acids, including polymer weight to weight, being required for a stoichio
the ester-forming derivatives thereof, and/or two or metric reaction.
more dihydric alcohols and/or one or more dihydrox As would be expected, various inter-acting factors
ydicarboxylic acids may be employed. Of particular in?uence the rate of the depolymerization reaction,
note in addition to polyethylene terephthalate are poly which factors where regulatable' must be controlled in
tetramethylene terephthalate and copolyesters formed accordance with the variables resulting from their ma
 3,884,850
7 8
nipulation as well as desired results. The minimum op molecular weight polyester can be selected from oligo
erable temperature under atmospheric pressure condi mer or monomer compositions in which the polyester
tions has been found to be the boiling point of the gly is soluble at the temperatures employed under atmo
col. Below this temperature, sufficient energy, with re spheric presure conditions. Of course, where the depo
sulting molecular cleavage, bombardment and the like, lymerization is part of a continuous polyester-forming
is not generated within the system to sustain a continu process with depolymerizate being continuously pre
ous reaction and/or the rate of reaction is too slow. The pared and fed with virgin monomer, i.e., 5 to 100 per
upper temperature limit cannot be stated with preci cent by weight depolymerizate, into polymerization
sion, depending upon the chemical and physical char and/or polycondensation systems, the solvent should be
acteristics of the particular polyester and glycol in formed from the same glycol and dicarboxylic acid as
volved. However, the skilled technician can readily rec the polymer to be depolymerized, and repolymerized
ognize the desired upper limit of temperature because during high molecular weight development phases of
the vapor pressure of the glycol will suddenly begin to the process. 1
rise at such a rapid rate that a high percentage of gly Considering depolymerization of polyethylene tere
col, ranging up to about 50 percent based on feed gly 15 phthalate, the preferred solvent will be selected from
col, will be lost in the vaporous effluent. A rough guide half ester (monohydroxyethyl terephthalate), ester
to bear in mind to indicate the approximate optimum [bis-(hydroxyethyl) terephthalate], oligomers, and low
temperature will be to calculate the mean temperature molecular weight polyesters in liquid phase at the tem
between the boiling point of the glycol and the temper perature of depolymerization as de?ned above and
ature at which glycol losses rapidly rise to about 50 per 20 mixtures thereof. It is apparent that such a solvent will
cent. The temperature of reaction should be within a not interfere with the depolymerization or repolymeri
few degrees, i.e., about 0° to 10° centigrade, of the zation reactions and would be continuously and inher
mean temperature. The optimum temperature and resi ently generated during depolymerization to further
dence time are further refined by balancing color detereact with glycol and polymer. Of course, certain other
rioration caused by high temperature and long resi 25 compositions may be admixed with the solvent initially
dence time, and large glycol loss, against the higher employed for desired purposes, for example, viscosity
variability in the depolymerized oligomer when em regulation. To avoid interference with the depolymer
ploying a lower temperature and a shorter residence ization and/or repolymerization reaction sequences, as
time, and consequently a lower glycol loss. well as side-product formation, adjunctive solvents
The rate of glycolysis of polyethylene terephthalate should be selected from materials inherently present
at temperatures below about 220°C, i.e., 200°—220°C during either reaction, for example, dihydric alcohol
but still above the boiling point of glycol, decreases (ethylene glycol in the case of polyethylene terephthal
substantially allowing vaporization of signi?cant quan ate) and/or water. It should be ‘understood that the ini
tities of glycol prior to reaction. As temperatures reach tial charge of solvent, which is preferably a low molecu
the 250°—260°C and above ranges, even though the re lar weight oligomer mixture or essentially 100 percent “
action occurs almost simultaneously with glycol addi- ester, including the half ester, could contain in admix
tion, vaporization is even more rapid than rate of reac ture therewith, ethylene glycol. In such instance, of
tion requiring a large excess of glycol to sustain a con ' course, desired reaction temperature should be
tinuous depolymerization; Thus, with depolymerization reached simultaneously with injection of the scrap
of polyethylene terephthalate at atmospheric pressure polyester into the system. Similarly, the amount of gly¢
col employed at start-up, if signi?cant, should be in- .
with minimal glycol loss, the temperature should be cluded in calculating the rate of subsequent glycol ad
within the range of about 220°—_25'0°C and preferably dition.
about 230°—240°C. ’
The following examples are presented “to illustrate
Average residence time in the continuous process the invention and are not intended to limit the inven
should be as short as possible, as long as product uni 45
tion in any manner.
formity and degree‘of depolymerization desired are not
signi?cantly affected, to prevent undesired product dis- ‘
coloration. With polyethylene terephthalate and ethyl EXAMPLE I
ene glycol at the preferred temperature range, a 1.5-2
hour residence time enables production of a uniform
product melting at about 190°C and having a color To a stirred reactor under atmospheric pressure con
upon repolymerization comparable to virgin polymer. ditions maintained at 230°C and initially containing _1 .8
An excess residence time develops undesirable yellow pounds bis-(hydroxyethyl) terephthalate, chipped
ness in the monomer which is transferred to the poly 55 polyethylene terephthalate of surface dimensions as de
mer subsequently formed therefrom. Additionally, pro scribed and of about 0.67 intrinsic viscosity as mea
longed residence time appears to increase‘ the diethyl sured in ortho chlorophenol at 25°C and ethylene gly
ene glycol content of resultant polymer as compared ‘to ‘ col are continuously‘fed as described in Table I. Oligo
polymer prepared from virgin monomer and from re mer is removed at a rate to allow the indicated average
constituted monomer from a shorter residence time 60 residence times. Depolymerization of 1 pound of the
process under the same polymerization conditions. polyester chip to trimer (melting point of 203°C) theo
Polymer melting point, critical in many high tempera retically requires 0.1 1 pound of ethylene glycol. Glycol
ture applications, is depressed approximately 3°C for losses are calculated by ,substracting the quantity of‘gly
' each 1 percent increase in diethylene glycol content of col theoretically required to depolymerize the polymer ‘ A
the polymer. 65
to oligomer of the stated melting point from the actual
The solvent employed for initial solvation of the high amount added. '
 3,884,850
9 10
TABLE I

Glycol Feed Approx.

Residence Polyester (Pounds/ Oligomer . Glycol
Experi- Time Feed Rate pounds Melting Loss
ment (Hours) (lbs/hour) polyester) Range (%)
1A 1.5 1.65 0.19 195-205 35
1B 3 0.83 0.12 185-195 0

10
The oligomer from Experiment 1B is slightly discol This example compares properties of polymers pro
ored as compared with IA oligomer and virgin mono duced from virgin monomer and 100 percent
mer. This example illustrates the depolymerization pro depolymerizate monomer. It is seen that polymer prop
cess and the balance required between residence time erties are comparable and entirely suitable for most
and other process parameters for production of end-use applications. Of course, during continuous op
depolymerizate of desired properties. erations, only about 5 to 50 percent by'weight of
depolymerizate would be included within the feed to
EXAMPLE II the low polymerizer. Typical polymer values would be
Polyethylene terephthalate of 0.67 I. V. in chip form an intrinsic viscosity of about 0.5 to 0.8, free carboxyl
of surface dimensions as described is continuously de 20 end groups concentration of about 20 to 35 micro
polymerized utilizing the depolymerization system of equivalents/gram, diethylene glycol content of about 2
FIG. 1. In each case, the depolymerizer is initially to 4 percent, a~me1ting point of about 254° to 258°C
primed with 50 pounds bis-(hydroxyethyl) terephthal and a luminance minus yellowness rating of about 20
ate monomer. The results and process parameters are to 60. In fact, up to about 5 percent by weight reconsti- .
tabulated in Table II. 25 tuted monomer can be incorporated into a typical feed

TABLE II

Average Glycol
Depoly- Polyester Glycol Feed Mole % Oligomer
merizer Feed Rate Feed Pounds/ Diethylene Residence Oligomer Approx.
Experi- Tempera- Pounds/ Pounds/ Pounds Glycol in Time Melting ‘ Glycol
ment ture (°) Hour Hour Polyester Monomer (Hours), Range (°C) Loss (%)
11A 245 50 6 0.12 1.0 2.8 190-230 ' ' -11
11B 240 100 12 0.12 1.0 1.4 185-200 11 , _
11C 240 50 6 0.12, L5 5.0 190-210 11

This example shows that the small scale process of for polycondensation without an observable. change in
Example I can be scaled up to much larger (commer 40 the polymer values tabulated in Table III.
cial) size with reduced glycol losses and several oligo
EXAMPLE IV
mer melting ranges depending upon operating condi
tions. The stirred reactor,v of Example I is filled with 2.0
pounds of low molecular weight oligomer .of poly(1,4
EXAMPLE III
45 butylene terephthalate) and the temperature .is raised
The oligomer from Experiment IIC is polymerized by to 150°C to melt it. Poly-(1,4-butylene terephthalate)
having an RV of 25** is continuously fed to the reac
a two—stage polycondensation consisting of a ?rst stage
low polymerization for one-half hour at 265°C under a tor, which is maintained at a temperature of 242° to
pressure of 30-40 mm Hg and a second stage high poly 245°C, at a rate of 0.56 pounds per hour while 1,4
merization for 4 hours at 283°C under an increased 50 butanediol is fed at a rate of 0.18 pounds per hour. De
vacuum of 2.0 mm Hg. Polymer characteristics are polymerized polymer is removed at 0.62 pounds per
compared with polymer produced from direct esteri? hour, thus providing a residence time in the reactor of
cation virgin monomer under the same process condi 3.6 hours. The melting range of the low molecular
tions in Table III. weight oligomer collected from the reactor stabilizes in
55

TABLE III

POLYMER CHARACTERISTICS
COOH Mole Lumi
(Micro- Percent nance
Intrinsic cquiva- Diethy- Melting Minus
Viscosity lents/ lcne Point Lumi- Yellow— Yellow
gram) Glycol (°C) nance* ness* ness

Polymer
from
Virgin
Monomer 0.69 35 1.35 259.8 60 8 52
[1C 0.62 25 2.35 257.5 63 34 29

‘As determined hy the Colormztster method. A luminance minus yellowness value within the range of above
about 20 is acceptable for further processing into shaped articles. i.c. ?lms and ?laments.
 3,884,850
11 12
the range l70°-l 84°C. This calculates to be approxi- hydric alcohol but below the melting point of said poly
mately tetramer. The relevant data for this example is ester and continuously recovering lower molecular
given in Table IV. weight depolymerizate.
measured at a concentration of 8 g/ld in orthodichlorophenol at 2. The process of claim 1 wherein Said polyester is Se_
5 lected from the group consisting of polyethylene, poly

TABLE IV

1,4 Butane- ,
Reactor Polymer diol Oligomer
Tempera- Residence Feed Feed Melting Glycol
lure Time Rate Rate Range Loss
242- 0.56 0.18 |70-|84°C
245°C 3.6 Hrs. Pound] Pound/ Average 66%*
Hour Hour

*mostly to tetrahydrol‘uran

The tetrahydrofuran loss can be minimized by adding trimethylene and polytetramethylene terephthalates.
tetrahydrofuran suppressants to the reactor, as is 20 3. The process of claim 1' wherein the polyester is
known to those skilled in'the art. - polyethylene terephthalate and the temperature of de
The above example demonstrates the utility of this polymerization is within the range of about 220° to
atmospheric depolymerization process for providing 250°C,
10W molecule“ Weight oligomers of other Polymers, and 4. The process of claim 3 wherein the temperature is
indicates the broad utility of the process for polyesters. 25 about 230° to 245°C
The optimum temperahh'e of reaction for holytetra' 5. The process of claim 4 wherein the solvent is bis
methylene terephthalate depolymerization is deter- (hydroxyethyl) terephthalate.
mined as discussed hereinbefore for polyethylene tere- 6_ The process of claim 1 wherein the average re“
phthalate’ and typically will be within the range of dence time in the depolymerizer is about 1 to 5 0 hours
about 230°C to 250°C, preferably 230°C to 240°C. . . ' .‘
Various modi?cations of the invention will appear 30 7' The process of clam 1 wherem the polyester is
obvious to those skilled in the art. polytetramethylene terii'phthalate'. . . - '
what is claimed is: 8.‘The process of claim 1 wherein the dihydric alco
1. A ‘process for continuously depolymerizing high h0l_ ls u_sed m an amount 0? “P to ab?“ 15 ‘percent by
molecular weight linear'pol'yester scrap said polyester 35 we'ght m excess of the §tolchlomemc requhément
being the polycondensation product of a dihydric alco- 9' A Process for contmuously depolymenzmgyoly
hol and a dicarboxylic acid comprising dissolving said ethylene terehhthalate SFraP t_° ah ohgomer mlxture
polyester scrap at an elevated temperature in a solvent which compl'lses Chargmg bls'(hydroxyethyl) tere
which is liquid'at the dissolving temperature, said sol- phthalate to a depolymerizer _ operating at_ about
vent being selected from the group consisting of mono- 4O 220°-250°C under atmospheric pressure, continuously
meric ester, bisester, low molecular weight esters and adding said polyethylene terephthalate and an amount
oligomers of said high molecular weight polyester to of ethylene glycol up to about 15% by weight in excess
form- a depolymerization mixture, continuously adding of that required for stoichiometric depolymerization-to
with said scrap polyester, dihydric alcohol correspond- an oligomer mixture of average chain length of about
ing to the. dihydric alcohol of said polyester scrap in a 45 2 to 3 monomer units based on terephthalic acid and
stoichiometric excess'sufficient to produce the desired a sufficient amount for maintenance of a continuous
degree of‘ depolymerization to at least an oligomer, ef- reaction to said depolymerizer, and continuously re
fecting s'aid‘depoly'rnerization under atmospheric pres- covering said oligomer mixture therefrom. I
sure at a temperature above the boiling point of said di- * * * * *
‘ i ' i 50

55

6O

65