PlainSite
Legal Document
®
Cover art © 2015 Think Computer Corporation. All rights reserved.
Learn more at http://www.plainsite.org.
United States Patent and Trademark Office Case No. 10721684
Multi-component Catalyst System For The Polycondensation Manufacture Of Polyesters
Document
View Document
View Docket
EXPRESS MAIL LABEL NO
.EV399608645US
PATENT ATTORNEY DOCKET
NO-P27,267-A USA
A MULTI-COMPONENT CATALYST SYSTEM FOR
THE POLYCONDENSATION MANUFACTURE OF POLYESTERS
[0001] This application is acontinuation-in-part ofapplication Serial
No.
5 10/303,977, filed
November
26, 2002,incorporated by reference herein.
TECHNICAL FIELD
[0002] This invention relates to
new multi-component
catalyst systems for the 10 polycondensation ofpolyesters. Ina particular aspect, this invention pertains tonovel
multi-component germanium
based catalystsystems for the polycondensation ofPET
(polyethylene terephthalate)used inthemanufacture
ofbottles, fibreand
film.
15
BACKGROUND OF THE INVENTION
[0003] It is well
known
inthepolycondensationcatalyst field that there are threeprimary
polycondensationcatalysts, basedon
the metals titanium,antimony and germanium. Titanium
(Ti) displays the highest activitybut ithas the disadvantage20
that itgenerates a large range ofundesirable side reactionswhich produce
apolymer
with a problematic yellow discoloration.
For
instance, in the caseof
polyethylene terephthalate polymers,once
thepolymer
is formed, it is very difficult to colour correct.25
[0004]An antimony
(Sb)based
catalyst, suchasantimony
trioxide, is themost
commercially used type ofcatalyst.However,
ittoo requires color correction. Thisisbelieved to be
due
tothe fact that particulateantimony
remains in thepolymer
thereby resulting ina grey discoloration inthe polymer.There
is agrowing
health concern issuethat relates to the use ofantimony
inmanufacturingpolymers
that will30
contact food.Such
foodmay
thereby absorb antimony. Additionally there aresignificant environmental concerns regarding the disposal of
an
antimony-containingdistillate
which
is an inevitable by-product ofthe polycondensation reaction.Finally, there are considerable environmental issues relating to up-stream processing of
antimony
catalysts.35
[0005]
Germanium
(Ge),from
a chemicaland polymer
discoloration viewpoint, hasno
negative implications as a polycondensationcatalyst.However, germanium
is costlyand
its cost is prohibitive to all but the highest qualitypolymer
producers.Significant research has
been
invested in thediscoveryof
catalyst formulations-2-
which combine
the benefits ofthethree catalystelements describedabove
whilst at thesame
time eliminating undesirablecharacteristics. In the case ofgermanium,
this essentially has led to the incorporation ofadditional activeelements or
com- pounds which
maintain catalytic reactivity butreduce cost without adversely5 affecting the
polymer
quality. Inmuch
ofthe prior art,germanium
has traditionallybeen used
as acomponent
to increase the quality ofpolymer produced by
catalysts such as titanium or antimony.[0006] Prior literature discloses
many ways
of addinggermanium
toa 10 polycondensation reaction.For example
Japanese patentJP 2001019753A2
published January 23, 2001, assigned to
Meldform
Metals, details thecomplexing
ofgermanium
dioxide with a range ofcarboxylicacids, toproduce an aqueous
solution containinggermanium
dioxide in aconcentration of 10 to20
wt.%.
15 [0007]
Other
patentshave
disclosed the use ofsynergistic catalyst enhancers, containing carboxylic acids, incombination with titanium-containing catalysts.For
instance, U.S. Patent
No. 6,372,879 Bl,
granted April 16, 2002, assignedtoATOFINA Chemicals
Inc., describes a range ofsynergistic combinations witha titanium-containing catalystand
lithium, sodium, potassium, rubidium, cesium,20
beryllium,magnesium,
calcium, strontium,barium and ammonium
salts.[0008]
U.S.
PatentNo. 6,258,925
Bl, granted July 10, 2001, assigned toATOFINA,
discloses a titanyl oxalate catalystand
a catalyst enhancersuch
as a metallic oxalate, for example, lithium oxalate.25
[0009]
WO 00/71252 Al,
publishedNovember
30, 2000, assignedtoACMA
Limited, discloses a catalyst composition for use in the preparation
of
esters, comprisingan
organometalliccompound which
is a reaction product ofan
orthoester orcondensed
orthoester oftitanium, zirconium oraluminium,
used in30
combination with acompound
ofgermanium, antimony
or tin. In this case, the preferred orthoester has the formulaM(OR)
4 orAl(OR)
3where M
is titaniumor zirconiumand R
isan
alkyl group,and
thecondensed
orthoestertypically being of the formulaR
10[M(OR
1)20]nR
1.
These
organometalliccompounds
arepreparedby
reacting the orthoesterand
the metalliccompound
in the presenceof, preferably, a 35 dihydric alcohol such as 1,2-ethanediol.[0010] U.S. Patent
No. 6,365,659 Bl,
granted April 2, 2002, assigned toToray
Industries Inc., discloses a polyester composition comprisinga polyesterand
acompound
oxide oftitanium as an essential elementand
a metal elementselectedfrom
thegroup
consisting ofaluminium,
zirconiumgermanium,
tinand
silicon.5
Specific particle size distribution for these catalysts inthe polyester is stated.[0011]
WO 0156694 Al,
publishedAugust
9, 2001, assigned toACMA
Limited,discloses thecombination of
an
organometalliccompound
containingeither titanium or zirconium with a second metalfrom
thegroup
consisting ofgermanium,
tinand
10antimony and
a carboxylic acid. In the preferredembodiment
ahydroxy
alcoholand
a baseare also present.[0012]
WO 9322367 Al
/EP0591488A1,
assigned toRhone Poulenc
ViscosuisseSA,
refers to adual polycondensationcatalystsystem
comprising lithiumand
15germanium. The
invention concerns amethod
ofproducing, without using anti-mony,
a polyesterfrom
poly(ethyleneterephthalate) units.Following
esterification, amixed
catalyst consisting of 10to75
parts permillion oflithiumand
15 to80
parts per million ofgermanium
isused
forpolycondensation.The
antimony-free polyester thus obtainedis purportedly suitable foruse inthemanufacture
ofbottles,20
sheeting, film, fibre, filamentsand molded
articles.[0013] U.S. Patent
No.
5,417,908, assigned toRhone Poulenc
ViscosuisseSA,
grantedMay
23, 1995, describes a polyestermanufactured
usingmanganese
as an esterification catalyst, de-activating themanganese
with phosphoric acidand
25
subsequently addinggermanium
as theprimary
polycondensation toform
apolyeth- ylene terephthalate polyester.[0014]
WO
99/28033, assigned toTioxide Specialities Limited, discloses theuse ofan
organometallic catalystwhich
is a reactionproduct ofan
orthoester orcondensed 30
orthoesteroftitanium,zirconium
oraluminium,
analcohol with at leasttwo
hydroxy
1 groups,an organophosphorous compound and
a base.[0015] U.S. Patent
No. 6,358,578 Bl,
assigned toZimmer AG,
grantedMarch
19, 2002, describes a productwhich
uses high surface area activated charcoal to35 promote
the activity ofapolycondensation catalyst such as antimony, titanium, lead,germanium,
zincand
tin.-4-
[0016] U.S. patent application
No. 2003/0045673 Al,
publishedMarch
6, 2003,Nakajima
etal., filedDecember
25, 2000, discloses a polyester polymerization catalystcomprising at leastone
kind selectedfrom
thegroup
consistingof aluminum and compounds
thereof as a firstmetal-containingcomponent,
characterized in that 5 the thermal stability parameter (TS) of polyethylene terephthalate(PET) polymer-
ized
by
the polyester polymerization catalyst satisfies the following formula (1):TS<0.30
(1)wherein TS
is anumerical value calculated inthe formula;TS=0.245{[IV]
f1A7-[IV];147} 10from
the final intrinsic viscosity ([IV]f)
which
is determined after 1g
Pet havingan
initial intrinsic viscosity ([IV]j) of approximately 0.65 dl/g is placed in a glass test tube,
vacuum-dried
at130°C
for 12 hours,and
maintained inamolten
stateat300 °C
for2
hours ina non-circulating nitrogenatmosphere
15
SUMMARY OF THE INVENTION
[0017]
The
catalyst systems according to the invention arenew
types ofpolycondensation catalysts
and have
particular applicationto the polycondensation reaction ofthemonomer
bis-hydroxy-ethyl terephthalate(BHET)
at elevated20
temperatureand
reduced pressure toproduce
high quality polyethylene terephthalate (PET).The
catalystsystems described herein arecomprised
ofa coregermanium
catalyst
and one
ormore
specified enhancers.[0018]
A multi-component
catalystsystem
for the polycondensation ofa polyester25 monomer
comprising the elementgermanium and one
ormore
catalyst enhancersselected
from
thegroup of
elements consisting ofone
ormore
ofaluminium,
silicon,
molybdenum, manganese,
lithiumand
combinations thereof, excepting the combination ofgermanium and
lithium only, said elements being intheform
of polycondensation compatible acids, bases,compounds,
salts, compositions, oxides30
or organic complexes.The monomer may be
bis-hydroxy-ethyl terephthalate,which
canbe
polycondensed
toproduce
polyethyleneterephthalate.[0019]
When
thecatalystsystem
comprisesgermanium and aluminium,
the levelof germanium
in the polyethylene terephthalatecanbe
inthe rangefrom
1 part per35
millionto200
parts per millionand
the level ofaluminium
inthe polyethyleneterephthalatecan
be
inthe rangefrom
1 partper million to400
parts per million.More
specifically, the level ofgermanium
can be 5 to100
parts permillionand
thelevel of
aluminium can
be20
to200
parts per million. Preferably, the level ofgermanium can
be 5 to60
parts per millionand
the level ofaluminium can be 60
to150
parts per million.5 [0020]
When
the catalystsystem
comprisesgermanium and
silicon, the level ofgermanium
in the polyethyleneterephthalate canbe
inthe rangefrom
1 partper millionto200
parts per millionand
the level ofsilicon in the polyethylene terephthalatecan
be inthe rangefrom
1 partper millionto400
parts per million.More
specifically, the level ofgermanium
canbe
10 to80
parts per millionand
the 10 level ofsilicon canbe
10to200
parts permillion. Preferably, the level ofgerma-
nium can be 20
to60
parts per millionand
the level ofsiliconcan be 20
to150
parts per million.[0021]
When
the catalystsystem
isgermanium and molybdenum,
the level of 15germanium
in the polyethylene terephthalate can be 1 to200
parts per millionand
the level of
molybdenum
in thepolyethylene terephthalate canbe
1 to200
parts per million.More
specifically, the level ofgermanium can be
1 to100
partsper millionand
the level ofmolybdenum
canbe
1 to100
parts per million. Preferably, the level ofgermanium can be
5 to60
parts per millionand
the level ofmolybdenum 20
canbe
1 to60
parts per million.[0022]
When
the catalystsystem
comprisesgermanium and manganese,
the levelof germanium
inthe polyethylene terephthalate canbe
1 to200
partsper millionand
thelevel ofmanganese
inthe polyethylene terephthalatecan be
1 to400
parts per25
million.More
specifically, the level ofgermanium can be
10 to80
parts per millionand
the level ofmanganese can
be 10to200
parts per million. Preferably, the level ofgermanium can be 20
to60
parts per millionand
the levelof manganese
canbe 20
to150
parts per million.30
[0023]When
the catalystsystem
isgermanium and
lithium,and one
ormore
of aluminium, silicon,molybdenum and manganese,
the level ofgermanium
inthe polyethylene terephthalate canbe
1 to200
parts per millionand
the level oflithium inthe polyethylene terephthalate canbe
1 to200
parts per million.More
specifi- cally, the level ofgermanium can
be 5 to60
parts per millionand
the level of35
lithiumcan be
10 to80
parts per million. Preferably, the level ofgermanium
canbe
5 to30
parts permillionand
the level oflithium canbe 20
to70
parts per million.-6-
[0024]
When
the catalyst systemscomprise germanium, aluminium and
silicon, orgermanium, aluminium and molybdenum,
orgermanium, aluminium and manga-
nese, or
germanium, aluminium and
lithium, orgermanium,
siliconand molybde- num,
orgermanium,
siliconand manganese,
orgermanium,
siliconand
lithium, or 5germanium, molybdenum and manganese,
orgermanium, molybdenum, and
lithium, or
germanium, manganese and
lithium, the level ofgermanium
inthe polyethyleneterephthalatecan be
in the rangefrom
1 partper millionto200
parts permillion, the level ofaluminium
inthe polyethylene terephthalatecan be
inthe rangefrom
1 partper million to200
parts per million, the level ofsiliconcan be
1 10 partper million to200
partsper million, the level ofmolybdenum can be
1 partpermillionto
200
parts per million, the level ofmanganese
canbe
1 partper millionto200
parts permillion,and
the level oflithiumcan
be 1 part per millionto200
parts per million.15 [0025]
The
catalystsystem
can alsocomprise germanium, aluminium,
siliconand molybdenum,
orgermanium,
aluminium, siliconand manganese,
orgermanium, aluminium,
siliconand
lithium orgermanium,
silicon,molybdenum and manganese,
orgermanium,
silicon,molybdenum and
lithium, orgermanium, molybdenum, manganese and
lithium, orgermanium, aluminium, molybdenum and manganese,
or20 germanium,
aluminium,manganese and
lithium, orgermanium,
silicon,molybde-
num and manganese,
orgermanium, aluminium, molybdenum and
lithium, orgermanium,
silicon,manganese and
lithium, orgermanium, aluminium,
silicon,manganese and molybdenum,
orgermanium,
aluminium, silicon,manganese and
lithium, orgermanium,
silicon,manganese, molybdenum and
lithium, orgerma- 25 nium,
aluminium, silicon,molybdenum and
lithium, the level ofgermanium
inthepolyethyleneterephthalate can be inthe range
from
1 part per million to200
parts per million, the levelofaluminium can be
in the rangefrom
1 part permillionto200
parts per million, the level ofsilicon in thepolyethylene terephthalatecan be
in the rangefrom
1 partper millionto200
parts permillion, the level ofmolybdenum 30
inthepolyethylene terephthalate canbe
inthe rangefrom
1 part per million to200
parts per million
and
the level ofmanganese
inthe polyethylene terephthalatecan be
in therange
from
1 partper million to200
parts permillion,and
the level oflithium inthe inthe polyethylene terephthalatecan be
inthe rangefrom
1 partper million to200
partsper million.35
[0026]
The
invention is also directed to amulti-component
catalystsystem
for the polycondensation ofa polyestermonomer
comprising the elementgermanium and
the catalyst enhancers
aluminium and
lithium, said elements being intheform
of polycondensation compatible elements,compounds,
acids, bases, salts,composi-
tions, oxides or organic complexes.
The monomer
canbe
bis-hydroxy-ethyl terephthalate,which
can bepolycondensed
toproduce
polyethylene terephthalate.5
[0027]
The
level ofgermanium
in the polyethylene terephthalate can be inthe rangefrom
1 partper million to200
parts per million, the level ofaluminium
inthe polyethylene terephthalate can be inthe rangefrom
1 part permillion to200
parts per millionand
the level oflithium in thepolyethylene terephthalatecan
be inthe 10 rangefrom
1 part permillion to200
parts per million.[0028]
More
specifically, the level ofgermanium can be
5 to100
parts per million, the levelof aluminium can be 20
to200
partsper millionand
the levelof
lithiumcan be
10 to80
parts per million.[0029]
Even more
specifically, the level ofgermanium
canbe
5 to30
parts per million, thelevel ofaluminium
canbe 60
to150
parts permillionand
the level of lithium canbe 20
to70
parts permillion.20
[0030]Without
attempting toprovidean
exhaustive list, thealuminium can be
incorporated inthe catalystsystem as aphenoxide, a lactate, a stearate, a glycolate, an oxalate, acitrate or atartrate.Without
attempting toprovidean
exhaustive list,the lithium
can
be incorporated inthe catalystsystem
as a hydroxide, an acetate, a citrate, a carbonate oran
oxalate.25
DETAILED DESCRIPTION OF THE INVENTION
[0031]
Throughout
the followingdescription, specific details are set forth in order to provide amore
thorough understanding ofthe invention.However,
the invention30 may be
practiced without theseparticulars. In other instances, wellknown
elementshave
notbeen shown
or described in detail to avoidunnecessarily obscuring the invention. Accordingly, the specificationand drawings
are tobe
regarded inan
illustrative, ratherthan a restrictive, sense.
35
[0032]We have
discovered that arangeof
specific elements,which
independentlyshow
limited catalytic activity, cansignificantlyenhance
the activity ofgermanium
as a polycondensation catalyst.
For
thepurposesof
thisdisclosure,we have
- 8 -
described theseelements as "enhancers". It is understood that the
term
"enhancer"includes
any
element or substancewhich
improves theperformance
ofa polyester condensationcatalyst notwithstanding that the element or substance per semay have
limitedcatalytic activity.A
synergistic relationship hasbeen
discoveredbetween
5 these catalystenhancersand germanium-based
catalysts.We have found
thataluminium,
silicon,molybdenum
ormanganese
used either independently withgermanium
or inamixed combination
(which can include lithium) exhibits a high catalyst activitywhen compared
toaPET
polycondensation product catalysedby germanium
only, or the activity ofthe enhancer only, or thesum
oftheir independ- 10 ent activities. This synergistic effect enables apolycondensationpolymer
of highquality tobe
produced
without entailing the costs normally associated with agermanium
only-catalysed polymer.[0033] It should be understood that in the discussion herein,
and
inthe claims,when
15
we
refer to the elementsgermanium,
aluminium, silicon,molybdenum, manganese and
lithium,we
are referring to the use ofthoseelements inany
conceivable polycondensation catalyst system, includingbutnot limited to the acids, basesand
salts ofthese elements, compositions containing these elements,
compounds
incor- porating these elements, oxides or organiccomplexes
ofgermanium and
the catalyst20
enhancers aluminium, silicon,molybdenum, manganese and
lithium. It is under- stood that in referring to the foregoing elementsand
substances,we
are contemplat- ingonly those elementsand
substances thatare compatible with polyesterpolycondensation systems inthe quantities
and
formswhich
catalyse the polycondensation ofpolyester.25
[0034]
The
use of our catalyst enhancers inappropriateamounts and forms
reduces thegermanium
requirementand
thereby reduces catalyst costthereby enabling the benefits of germanium-catalysedPET
to be gained inmarketswhich
otherwisewould be
excludedon
a cost basis.We have
found that itis possible according to30
the inventionto maintainoptimum
catalyst quality. It is also possible after adjust-ment
ofthe ratios ofthe respectiveelements toproduce
an antimony-free alternative catalystsystem
at acompetitive cost.[0035]
Examples
ofcatalyst combinations that demonstrate the subject invention are35
given in Table 1.However,
it shouldbe
understood that thoseexamples do
notrepresent the full range ofcatalyst levels
which have
displayed the synergisticeffectand
accordingly the scope ofthe invention is not limited thereby. It should also beunderstood thatthe combinations
which
demonstrate the highest levels ofcatalytic activitydo
not necessarilyproduce PET
with themost
preferred characteristics.For
thepurposes ofthese testsgermanium
content in the polyester hasbeen most
preferably
used
inthe rangefrom
5 to60
parts per million.However,
beneficial 5 effectshave been
observed in the rangefrom
1 to200
parts permilliongermanium.
[0036]
For aluminium
incombination
with agermanium
catalyst, synergy hasbeen
observed inthe rangefrom
1 to400
parts per million.However,
the preferable range ofaluminium
is20
to200
parts per millionand
ideally60
to150
parts per 10 million,dependant upon
the levelsof
the catalystemployed.
[0037]
For
silicon in combination with agermanium
catalyst, synergy hasbeen
observed inthe rangefrom
1 to400
parts permillion.However,
the preferable range ofsiliconis20
to200
parts permillionand
ideally60
to150
parts per 15 million,dependant upon
the levels ofthecatalystemployed.
[0038]
Molybdenum
hasbeen
investigated in combination withgermanium
inthe rangefrom
1 to200
parts per million levels with significant catalytic activity being observed atlow
levels, specifically with the level ofmolybdenum
being inthe range20
or 1 to 100parts permillionand
themost
preferred range being 1 to60
parts permillion
molybdenum.
[0039]
Manganese
has displayedgermanium
enhancer properties inthe rangefrom
1to
400
parts per million,more
specifically 10 to200
parts per million,and
themost 25
preferredbeing inthe rangefrom 20
to60
parts per million.[0040]
Lithium
incombination withone
ormore
ofaluminium,
silicon,molybde-
num and manganese
has demonstratedgermanium
enhancer activity in the rangefrom
1 to200
parts per million, themost
preferred levels being 10to80
parts per30
millionand
ideally20
to70
parts permillion.[0041] Itshould
be
understood that these optimized catalyst loadings aredependent upon
thegermanium
level, and, particularly withrespect to catalystsystemsincluding
two
ormore
enhancers, the othercomponents
within thesystem.35
[0042]
A primary
advantage ofthegermanium
enhancerswe have
discovered isthatit is possible to obtainhigh quality
polymer manufactured
using reducedgermanium
-
10-
levels. Therefore, asignificantbenefit ofour catalyst
system
accordingto the invention is reduced costand
the opportunity for replacement ofheavy
metal catalysts inlower
value applications.Without
being adverselybound by any
theories, but inthe interests ofexplaining the invention,
we
believethat novelty in 5 the invention resides inthe synergistic effectson
thecatalytic activity thatwe have
observedwhen combining
the previouslymentioned
catalyst enhancers withgerma-
nium.We have
described the elements as catalyst enhancers rather than catalystsdue
to their relatively limited activitywhen
used independently,compared
with the remarkable activity thatwe have
discoveredwhen
they areused in combination with 10germanium. The
enhancer elementswe have
discoveredhave
not toourknowledge
been
demonstrated within the prior artand have
negligible independent catalytic activity, but surprisingly display significant levelsof
activitywhen combined
withgermanium.
15 [0043]
Advantages
ofthe catalyst systemswe have
discovered are fast reactionrate,lowercost,
lower
catalyst (metal) addition,and comparable polymer
quality tocommercial PET
products usingcommercially
available catalysts.EXAMPLE
120
[0044] Catalyst testing
was
carried usinga conical5-L
stainless steel oil-jacketed reactionvessel.The
experimentswere
carried outat a controlledmelt temperature of280° C and
atpressures oftypically less than 1mbar. The
reaction meltwas
agitated
by
averticallymounted
helical stirrer operatingat a constant speed (10025
rpm).The
stirrermotor'samperage was
monitored.The
reaction is considered tobe complete
when an amperage
generating a torque equivalent toan
intrinsic viscosity of 0.6 is attained. (Intrinsic Viscosity (IV), isan
indication ofpolymer
chain lengthand
thus degree ofpolymerisation.) Distillates generatedby
boththe pre-polycondensationand
the poly condensation stepswere
collected separately.30
Catalyst-freeBHET
(bis-hydroxy-ethyl terephthalate)was
typically used eliminating theneed
for the suppressionofesterification catalysts. Catalystsand
stabiliserswere added
to the vessel atthe time ofBHET
chargingand
airwas removed from
thesystem
prior to thereactioncommencing.
Informationrelating to theoiland
reaction temperatures, the pressure within the vessel, the stirrer speedand
torque35 was
automatically logged every 10 seconds to enable accurate batch to batchcorrelation to
be
attained.For comparison
calibrationpurposes, testbatchescontaining commercially available germanium-containing catalysts
were
periodicallycompleted.
These
experiments provided a catalyst activity template againstwhich
different catalyst systems could beeasily
compared.
Typical reactiontimes for germanium-catalysed polycondensation overa range ofcatalyst loadings are described inTable
1 below. Table 1below
also tabulates results obtainedfrom
conducting polycondensation tests using various metals, alone or incombination.-
12-
Test
Number
fPatent
Ge
Template3AT
Catalyst
Type
Ge
OnlyGe
OnlyTABLE
1 Catalyst"ading
PPm TOO"
TOO"
Polyc n
Time
mins 343"
IV
T5F"
0.607
"A3"
10
15
20
25
30
35
40
45
50
"A4"
"A5~
~A6~
Ge
OnlyGe
OnlyGe
Only30"
30"
30"
"85T"
333"
32TT
105.5
0.612 0.608 0.635 0.608
~A7"
Ge
OnlySb
Only30" T043"
300"
108.20.624 0.603
"A8"
~A9"
"ATO"
"ATT"
"ATS"
~AT4~
~AT5~
"ATS"
"ATT
"ATS"
"AT5"
"A20~
"A2T"
"A22"
Li Only
LiOnly
AlOnly Ge/Al Ge/AI Ge/Al Ge/AI Ge/Al Ge/AI Ge/AI Ge/AI Ge/AI Ge/AI
Mo
OnlyMo
Only"
"200"
30" A
bandoned"Abandoned
12060/60 60/30"
Abandoned"
683
60/25 50/43 45/45 40/53 30/60 20/80 10/200 60/150
300"
333"
353"
303"
103.0 83.5
383"
93.6 133.7
"533"
111.6
0.613 0.616 0.603 0.618 0.623 0.624 0.615 0.600 0.586 0.608 0.578
"A23"
"A24"
Ge/Mo
60 60/60
TT8T"
"237T
0.575 0.560
"A25"
"A26"
Ge/Mo Ge/Mo
60/20
"6075"
303"
0.574353"
0.581"A27"
~A28"
Ge/Mo Ge/Mo Ge/Mo
3075 3075"
343"
3750"
353"
333"
0.578 0.573 0.560
"A23"
"A30"
Ge
Template2Ge/AI/Si Ge/AI/Li
45/45/15 45/45/45
373"
333"
0.6110.605npli
"BT~
"B2~
"B3"
34"
33"
36"
"BT"
38"
35"
Ge
OnlyGe
OnlyGe
OnlyGe
Only SiOnlyGe/Si Ge/Si Ge/Si Ge/Si
8cT
3D"
100.5
30"
"43"
115.7 TT677"
132.0
300"
60/155 60/20 40/103
"40734"
Abandoned 833 393"
107.2 123.0
0.594 0.610 0.602 0.618
0.591 0.580 0.592 0.608
3T0
BIT Mn
OnlyGe/Mn
300"
3072T
T333"
117.0
0.598 0.606
55 Al
0: Al only; 120 ppm
Alas
tartrateA9:
Li only;80 ppm as
oxalateThe term "abandoned"
intestsA8, A9, A10 and B5 means
that thetestswere
stopped after therewas no
increase in torque aftertwo
hours atthe standard60
polycondensation temperatureand
pressure.Test Criteria
and
Results of Testing[0045] All
BHET
usedwas
freefrom
esterification catalysts in order to eliminateany
potential interaction with the polycondensation catalysts tested.5 [0046]
Phosphorus was added
as athermal stabiliserand
insome
processes itwas
also
added
todeactivate esterification catalysts prior to beginning polycondensation.It is
known
thatphosphorus can
affect theactivity of polycondensationcatalystsand
therefore all testswere performed
with areasonable level (40 partsper million) ofphosphorus added
asH
3P0
4.10
[0047] Control samples containing
germanium
onlywere
tested toproduce
a template. Allnew
catalystswere
tested against agermanium-only
template of40
to100
parts per million addition.Care was
takentoproduce
anew
template followingany maintenance work on
thePET
reactorthatmight
affectthe process control 15 characteristics.The examples
describedshow
testsperformed
versustwo
templates(A and B) which were produced
followingachange
of temperature control equip- ment.[0048] Referring to Table 1, samples
Al
-A6 were
testedat 60, 80and 100
parts20
permilliongermanium
addition.The
reproducibility oftestswas shown
tobe
verygood. Also, a standard commercially available
antimony
catalyst (A7)was
tested in ordertocompare
activityand
total catalyst loading.Aluminium,
lithiumand
molybdenum were
tested againstthis template.Each
elementwas
testedon
itsown
and
incombination
withgermanium
at various levels.25
[0049]
Samples Bl
-B4 were
tested at40,60 and 80
parts per milliongermanium
addition.
The
reproducibility oftestswas shown
tobe
very good. Siliconand manganese were
tested againstthis template.Each
elementwas
testedon
itsown
and
incombination
withgermanium
atvarious levels.30
[0050]
During any
testcampaign, germanium-only
testswere performed
at regular intervals to ensureno
driftfrom
the template.Lithium
-Samples A8
-A9
35 [0051]
Lithium showed no
catalytic activityon
itsown even
at200
parts per million addition.When combined
withgermanium, however,
thegermanium
activitywas
enhanced. It appears that theenhanced
activity is limited, with approximately the-
14-
same
activity achieved withthe lithium addition variedbetween
10and 80
parts per million.Aluminium
-Samples A
10 -A20
5 [0052]
Aluminium showed
limited catalytic activityon
itsown. However, when combined
withgermanium, aluminium enhanced
the catalytic activity ofthegermanium.
Variousgermanium/aluminium
levels areshown,
each ofwhich shows
significantly
enhanced
activitycompared
with thesame
level ofgermanium on
itsown.
In fact,even
at20
partsper milliongermanium
addition(A
18), an equivalent 10 activity togermanium
only at80
parts permillion addition is achieved.At
thislevel, the activity is greaterthan astandard
antimony
catalystaddition of200
parts per million (A7),and
the catalyst contains only50%
ofthe metallic additionlevels as theantimony
catalyst,and
ismuch
less expensive thanthe equivalentgerma- nium-only
catalyst.15
Molybdenum
-Samples A21
-A28
[0053]
Molybdenum showed some
catalytic activityon
itsown. However, when combined
withgermanium, molybdenum enhanced
the catalytic activity ofthegermanium by
amuch
greateramount
thanwould be
expected basedon
themolyb- 20 denum
activityon
itsown.
Variousgermanium/molybdenum
levels areshown, each
of
which shows
significantlyenhanced
activitycompared
withthesame
level ofgermanium on
itsown.
In fact,even
at 5 parts per milliongermanium
addition (A28),an
equivalent activity togermanium
only atmore
than100
parts per million addition is achieved.At
this level, the activity ismuch
greaterthan a standard25 antimony
catalyst addition of200
partsper million, it contains only32.5%
ofthemetallic addition levels as the
antimony
catalyst,and
it ismuch
less expensive than the equivalentgermanium-only
catalyst.Silicon -
Samples B5
-B9
30
[0054] Siliconshows no
significant catalytic activityon
itsown. However, when combined
withgermanium,
siliconenhanced
the catalytic activity ofthegermanium.
Various germanium/silicon levels are
shown,
each ofwhich shows enhanced
activitycompared
with thesame
level ofgermanium on
itsown. At 40
parts per milliongermanium
addition (B8, B9),an
equivalent activity togermanium
only of50
to60
35 parts permillion additionwas
achieved.Manganese
-Samples B10
-Bl
1[0055]
Manganese showed some
catalytic activityon
itsown. However, when combined
withgermanium, manganese enhanced
the catalytic activity ofthegermanium by
a greateramount
thanwould be
expected basedon
themanganese
activity
on
itsown.
Variousgermanium/manganese
levelshave been
tested, each of 5which
demonstratedenhanced
activitycompared
withthesame
level ofgermanium
on
itsown. At 50
parts per milliongermanium
addition (Bll),an
equivalent activity togermanium
onlyof 60
parts per million additionwas
achieved.Multi-Component Samples
-A29-A30
10 [0056]
The
tests demonstrate thatgermanium
contentcan
be further reducedby combining
the"enhanced"
effect oftwo
ormore
ofthe additives previously described. TestsA29 and A30
contain thesame
addition levels ofgermanium and aluminium
as TestA
15.However,
the addition ofa furtherpromoting
element, silicon inA29 and
lithium inA30, enhanced
the activity furtherfrom
approximately 1560
parts per milliongermanium
only equivalent toaround 100
parts permilliongermanium
only equivalent.[0057]
The
information gainedfrom
the testson
the above-described reactorhave been
validatedby
external testson
both continuousand
large-scalebatch reactors.20 These
testshave
confirmed that, for the range of processand
chemical operating parametersused, there is complete correlation with industrial equipment.The
inventors are therefore confident that the invention is scientifically valid
and
is notdue
toany
specific characteristic oftheequipment
used.25 EXAMPLE
2[0058] Further tests
have been performed and have
provided the following data:Ge/Al-
Tests203 -210
[0059]
The
testsbelow
demonstratethe effecton
the activity ofthe catalystsystem 30
with variation in the ligand associated withthe Al.These
testswere
conducted inthe presence ofaphosphoric acid stabilizer
and
aphosphorus
level of40 ppm was
used.
[0060]
From
this data it is possible to conclude that withrespectto activity alone the35
preferred ligands are lactate or glycolate. Itshouldbe
notedthat effectsdue
to theligand chemistry can be observed in other
PET
parameters including but not limited to colorand
optical clarity ofthe final polymer.-
16-
PET Rig
CatalystType
CatalystPolycon IV
Test
No. Loading Time/Mins LSP
Ge/Al ppm
202 Ge
only 100/0 80.70.563
203 Ge/Al
(Al asphenoxide)30/100
79.1 0.531204 Ge/Al
(Al as isopropoxide)30/100
138.6 0.631205 Ge/Al
(Al as lactate)30/60
89.50.624
206 Ge/Al
(Al as stearate)30/100
115.60.596 207 Ge/Al
(Al as glycolate)30/100
81.30.596
208 Ge/Al
(Al as oxalate)30/100
92.10.603
210 Ge/Al
(Al as citrate)30/100
93.60.602
Ge/Al/Li
- Tests290
-299
[0061]
The
following tests demonstrate a similareffect to that observed with Al, in 15 this instance the ligand associated with the Liwas
variedand
the chemistry ofthegermanium and
thealuminium was
kept constant.[0062] Additionally, with the tests using lithium acetate the phosphoric addition
was
adjusted todeterminethe degree
by which
the activitywould be
effected.20
PET Rig
TestNo.
Catalyst
Type
CatalystLoading Ge/Al/Li
Polycon Time/Mins
P ppm
IV LSP
290 Ge/Al/Li
(Li asOH)
15/60/45 87.340
296 Ge/Al/Li
(Li as acetate) 15/60/45 71.840 297 Ge/Al/Li
(Li as acetate) 15/60/45 88.880 298 Ge/Al/Li
(Li as acetate) 15/60/4588 80 299 Ge/Al/Li
(Li as citrate) 15/60/45 110.9580
30
[0063] It is reasonable toconcludefrom
these tests that the preferred ligands associated with the lithiumwould be
either the hydroxide or the acetate.Ge/Al/Li
- Effect ofPhosphorus
- Tests274-278
PET Rig
TestNo.
Catalyst
Type
CatalystLoading Ge/Al/Li
ppm
Total
Time/Mins
P/ppm IV LSP
274 Ge/Al/Li
(Li asOH)
15/60/45 117.380 0.588
278 Ge/Al/Li
(LiasOH)
15/60/45 98.80
0.591[0064]
From
theabove
data (and in combination withthat displayed inthe foregoingtests involving
Ge/Al and
Ge/Al/Li) it is clear thata limited degree ofcatalyst 10 deactivationdue
toP
is observed. It isbelievedthat alevel ofP
enhances thethermal stability ofthe
polymer and
the observed levels ofdeactivation are consid- ered tobe
within acceptable limits.Colour
Information 15Sample L* a* b*
T269 Ge
only100 ppm
69.88 -0.48 2.88T274 Ge/Al/Li
15/60/45ppm
69.16 -1.58 6.41T278 Ge/Al/Li
15/60/45EST (No
Phosphoric)70.81 -1.6 6.8
T302 Ge/Al/Li
15/60/45EST (80ppm
P)lOppm Co
66.23 -1.1 1.3
[0065]
The above
color data is forpolymer which
hasbeen produced by 25
esterification/polycondensationon
the1.5Kg
laboratory reactorand
hasbeen
analyzed using a
HunterLab ColorQuest XE
Spectrophotometer according to theCIE 1976 L*a*b*
scale where:L*
is ameasurement
oflightnessfrom 100
for perfect white to0
for black;b*
is ameasurement
ofcolorwhich
trendsfrom
redwhen
positive to30
grey at zeroand
greenwhen
negative;and
a* is a
measurement
ofcolorwhich
trendsfrom yellow when
positive to grey atzeroand
bluewhen
negative.-
18-
[0066]