Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
WO97/17S19 PCT/EP~2/00669
~ ~ ~ 3~7 9
Hiqh molecular weisht copolyester resin5havin~ low melti~q
points
The present invention relates to high molecular
weight copolyester resins having low melting points and
peculiar crystallization behaviour and the process for
preparing the resins.
It is well known that the molecular weight of the -- -
polyester resins can be increased by solid state
polycondensation reaction.
The possibility however to upgrade polyester resins
having low melting points, e.g. lower than 220C presents
serious process difficulties due to the sticking problems
on the walls of the reactor caused by the high upgrading
temperatures used.
The known solid state polycondensation processes need
high upgrading temperature due tQ the low kinetic of the
upgrading reactions. Usually, the solid state
polycondensation reactions of polyester resins are per-
formed by temperatures higher than 180C; mainly higher
than 195C (see page 3295 of Journal of Applied Polym. Cs.
?8 3289 - 3300, 1989).
The possibility of preparing polyster resins with low
melting points and having sufficiently high values of the
intrinsic viscosity, which are particularly suitable for
extrusion blow applications, is a not yet solved problem.
In Applicant's previous pending European application
No. 89119049.8 a solid state upgrading process is
described in which the resin is upgraded at temperatures
hi~her than 170C nd in qeneral in the range of 170C
22QC, using a dianhydride of an aromatic tetracarboxylic
acid.- ~ -
The resins su~jected to upgrading comprise
copolyethylenterephtalates (COPETs). Amongs ~he COPETs use
is exemplified of copolimers containing at most 10% in
W092~17~19 PCT/E~2/00669
. .
mols of units deriving ~rom isophtalic acid on the total
of the acid units. Except the melting point of the resin
after upgrading and intrinsic viscosity values no other
indications are qiven regarding the upgraded polymer.
It has now been found that it is possible to upgrade
polyester resins havins melting points lower than 220C
without having sticking problems and that the upgraded
resin presents valuable properties particularly from the
viewpoint of the crystallization behaviour.
The resins subjected to upgrading are the
copolyethylenterephtalates containing from lO to 25% by
weight on the total resin weight of units deriving from
isophtalic acid (COPETs).
According to the process of the present invention,
the COPET is upgraded at temperature lower than 170C and
higher than the TG of the resin, preferably comprised
between 130 and 160C using an upgrading additive select-
ed from the group consisting of the dianhydrides of
aromatic, aliphatic cycloaliphatic tetracarboxylic acids.
Unexpectedly, the upgraded COPETs present, besides
the high IV values (higher than 0 85 dl/g) and molding
points lower than 220C, other valuable properties.
In particular the crystallization behaviour of the
resins is remarkable from the view point of the m~ding ;~
applications, because the resin does not show any
cristallinity also by slow cooling from the melt; the
COPETs give clear, transparent amorphous solids also by
very slow cooling rate, e.g. 1C/~in.
It is worthwhile to note that the resin crystallizes
when heated in the solid state for instance at l50C for
40 mins.
Another interesting property of the resin i5 its
gel-free characteristic. '
Par~icularly interesting is the COPE~ containinq
about lS~ weight o the resin of isophtalic acid units, -
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WO 92tl7~19 PCT/EP92/00669
3 ~.--
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melting point of 212C This COPET gives clear highlytransparent amorphous solid by cooling its melt also at
very slow cooling rate (l~C/min). Pyromellitic dianhydride
is the preferred upgrading compound.
Other suitable dianhydrides are the dianhydrides of
1, 2, 3, 4-cyclobutanetetracarboxylicacid,
3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic
acid and 3,3',44' ben~ophenone tetracarboxylic acid.
The preferred dianhydride from the cycloaliphatic
acids is 1,2,3,4 cyclobutantetracarboxylic acid
dianhydride.
Interesting results are also obtainable with the
dianhydride of 3,4 dicarboxy - 1,2,3,4
tetrahydro-l-naphtalenesuccinic acid and bicyclo (2,2,2
oct-7-ene 2,3,5,6 - tetracarboxylic acid.
The preferred concentration of the additive with
respect to the polyester resin is 0,05-1~ by weight.
The solid state upgrading process comprises the steps
of blending the COPET resin in a molten state with the
upgrading additive, converting the melt into granules,
crystallizing the qranulate at temperatures hiqher than
the TG of the resin but lower than 180~C and then upgrad-
ing the crystallized resin at a temperature co~prised in
the range from the TG of the resin and 180C, partlcularly
from 130 and 170 C.
The process is preferably carried out in continuous
way using continuous crystallizers and upgrading reactors
where the chips can move counter currently with a stream
of a heated gas, e.g. air, nitrogen and carbon dioxide.
Apparatus suitable for the crystallization and
upgrading steps can be those described in USP 4,064,112
and 4,161,578 whose description is herewith enclosed for
reference.
The recycling of the inert gas streams can be carried
out accordinq to European application 86830340.5 whose
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W092/17~19 PCT/E~t/00669
2 ¢ S~?~ 79 4
description is herewith enclosed for reference.
The blending of the polyester resin with the additive
is carried out in an equipment capable to perform reactive
extrusion such as corotating or counter rotating inter-
meshing or not intermeshing twin screw extruder with or
without venting capability at a temperature between 200~
and 350C, depending on the melting point of the
polyester.
A counter rotating non intermeshing twin screw
extruder vented or not vented is preferred.
The use of such kind of extruder allows to perform a
good distribution of the additive in the melt and to avoid
problems of local high concentrations of the additive due
to its high reactivity.
The extruder may be directly fed with molten COPET
from a plant in which the COPET is produced by
polycondensation in the molten state.
The extruder may also be fed with solid COPET granu-
lates produced in another plant.
The extruder is preferably connected to a high vacuum
oil seal pump to maintain a vacuum higher than 2 torr for
the devolatilization of the reactive blend and for obtain-
ing a resin with a low content of acetaldehyde. However,
the blending could be also performed without the use of
vacuum.
The residence time in the extruder could be comprised
between 10 and 120 sec., preferably 15-30 sec.
To avoid random local concentration of additive in
the melt it is advisable to dilute the additive with
crystallised PET powder (1 part of additive to 5 parts of
PET powder~. This procedure will ensure a homogeneous
-distribution of PMDA in the melt leading to a better
reproducibility of the end product intrinsic viscosity and
inhibiting the gel formation.
The dianhydride could be also diluted using blends of
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WO92/17~19 PC~/EP92/00669
.
~S~;'9
the dianhydride and crystallized PET-chips (l part addi-
tive to l0 parts PET chips). The dilution could be per-
formed in a fanned blender using about 0,l~ of
polyethylenglycol or polycaprolactone, as adhesives, and
using blending temperature at about 150C.
The reactive melt coming out of the twin screw
extruder is continuously pallettized using an underwater
pelletizer or a strand pelletizer system.
According to another aspect of this invention, the -
new COPETs may be modified by blending with polymers like
polybutylenterephtalate, polycarbonate, polycaprolactone,
polyester elastomers, phenoxy resins in amount up to about
20~ by weight of the total resins, directly before the
extrusion processing. The addition has the effect of
improving the mechanical properties of the composition as
well as the processing conditions without sacrifying the
transparency of the end product.
Analytical Procedures
The intrinsic viscosity was determined on a solution
of 0.5 g of COPET in l00 ml of 60/40 mixture by weight of
phenol and tetrachloroethane at 25C according to ASTM D
4603 - 86.
The acetaldehyde content was determined with a gas
chromatographic method according to ASTM D 4526-85, using
a Perkin Elmer 8700 gas chromatograph. (Perkin Elmer model
HS l0l).
The extraction conditions were 150C for 90 min.
Example l
30 Kg/h random COPET melt (l5~ isophtaiic acid in
weight, melting point 212C, IV = 0.75 dl/g) having a
content of ll0 ppm acetaldehyde were fed continuously from
the finisher of PET melt polycondensation pilot plant to a
counter rotating not intermeshing 30 mm twin screw extrud- ~-
er with venting capability. 1 -
220 g/h of a mixture of 20% weight of pyromellitic
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WO92/17519 PCT/E~2/00669
~3~9
acid dianhydride in crystallized COPET powder (IV: 0.75
dl/g, 15% weight isophtalic acid) were fed to the extruder
using a gravimetric feeder.
The test conditions were as follows:
- pyromellitic acid dianhydride in the COPET melt
0.15% by weight
- screw speed: qlS RPM
- ratio length/diameter (L/D): 24
- average residence time: 18 - 25 sec.
- barrel temperature: 235~C
- product melt temperature: 290~C
- vacuum: 1 - 5 torr
A die with double holes was used as extruder die (Diame-
ter: 7 mm).
A strand pelletizer was used to obtain the COPET-
chips which had a cylindrical shape with a diameter of 3
mm and a length of S mm, and with an intrinsic viscosity
IV = 0.85 + 0.01 dl~g.
The COPET chips had an acetaldehyde content of 5 - 8
ppm. During the test period, the IV of the product was
constant over the period of 2 weeks.
The melting point of the product was 212C.
The COPET-chips were then fed continuously to a solid
state upgrading pilot plant using the apparatus and the
inert gas ricycling conditions set forth in European
application EP 86830340.5.
The crystallization temperature was 150~C and the
residence time was 40 min.
The temperature of the solid state upgrading reactor
was 150C and the residence time was 12 h.
The IV of the upgraded products was 0,94 + 0,02 dltg.
The product was free from gel, with acetaldehyde
content of 0.60 ppm.
In comparison, there was no upgrading of COPET not
containing pyromellitic dianhydride (starting IV = 0.75
- - : . .: .. . . .. :. ... ... ... . . . .
W0~2/17~19 PCT/EP~2/00669
7 ;~S3~
l/g) using the same conditions for crystallization and
upgrading as in this example.
The crystallization behaviour of the COPET in compar-
ison with standard PET is shown in figure 1.
Fig. 1 shows the crystallization kinetic of COPET
prepared according to this example in comparison with
standard bottle grade polyethyleneterephthalate. The
crystallization kinetic was determined under isothermal
conditions at 120C.
It is interesting that although this COPET is
crystallizing in the solid state (150C/40 min), its melt
does not bring about any crystallization by coolin~, and
gives a clear transparent amorphous solid also by very
slow cooling rate.
Table 1 shows the data relating to crystallization by
cooling of COPET of example 1 in comparison to standard
PET.
All the crystallization data are obtained by DSC
measurements performed with Mettler Thermal Analyzer YC
11.
Fig. 2 reports the DSC curves of COPET versus the
cooling rate of the melt, starting from a rate of 10C/min :
changing then to 5 and 3C~min = curves A, B, and C
respectively. Curve 1 refers to standard PET cool~d to a
rate of 10C/min wherein the increase of the heat of
crystallization is 11.8 J/g.
TABLE 1
Heat of melting of PET samples crystallized with
different cooling rates.
Heats are in joule/gram.
.
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W092/17519 PCT/EP92/00669
~ ~ S ~ ?~;Jg 8
.
SAMPLE I QUENCHING I COOLING RATE (deg/min)
10 5 3
COPET I 2.1 (a) I N N N
I STANDARD PET I 30.0 (b) I 34.1 (c)
N = no crystallization
a) crystallization during melting 1.6 J/g
b) crystallization during melting 29.1 J/g
c) crystallization during melting 12.2 J/~
Example 2
30 Kg/h random COPET melt (15% isophthalic acid in
weight, melting point 212C, IV = 0.75 dl/g) having a
content of 110 ppm acetaldehyde were fed continuously from
the finisher of a PET melt polycondensation pilot plant to
a counter rotating not intermeshing 30 mm twin screw
extruder with venting capability.
220 g/h of a mixture of 20% weight of 1, 2, 3,
4-cyclobutanetetracarboxylic acid dianhydride in
crystallized COPET powder (IV: 0.75 dl/g, 15~ weight
isophthalic acid) were fed into the extruder using a
gravimetric feeder. The test conditions were as follows:
- C,yclobutane tetracarboxylic acid dianhydride in the
~ OPET melt = 0.15~ by weight
- Screw speed: 415 RPM
- R tio length-diameter (L/D): 24
- Average residence time: 18 - 25 sec.
- Barrel temperature: 235~C
- Produst melt temperature: 290C
- Vacuum: 1 - 5 torr.
- A die with double holes was used as extruder die
(Diameter: 7 mm).
A s~rand pelletizer was used to obtain the COPET-
chips which had a cylindrical shape with a diameter of 3
WO92/17519 PCT/EP92/00669
g ~S~
~m and a length of S mm, and with an intrinsic viscosity
IV = 0.865 + 0.0l dl/q.
The COPET chips had an acetaldehyde content of 6 - 9
ppm. During the test period, the IV of the product was
constant over a period of 2 weeks.
The meltinq point of the product was 212C.
The modified COPET-chips were then fed continuously
into a solid state polycondensation pilot plant using the
apparatus and the inert gas recycling conditions described
in European application EP 86830340.5.
The crystallization temperature was 150C and the
residence time in the crystallizer was 40 min. The solid
state temperature in the reactor was 150C and the resi~
dence time was l0 h. The IV of the upgraded product was
0,965 dl/g. The product was free from gel, with an
acetaldehyde content of 0.60 ppm.
In comparison, there was no upgrading of COPET not
containing the dianhydride (starting IV = 0.75 dl/g),
using the same conditions for crystallization and upgrad-
ing as in this example.
Example_3
The same COPET was used as in Example l, but in the
form of crystallized COPET granules of IV = 0.75 dl/g.
The crystallized COPET chips were dried and fed into
the twin screw.
The IV of the product was 0.845 + 0.02 dl/g.
The same conditions were used as in Example l; only
the average residence time was about 25 sec.
The solid state conditions were 130~ - 140-C in the
crystallizer and 140-C in the ,polyaddition reactor. The
residence time in the reactor was l0 hours. The chips
intrinsic viscosity was 0.92 + 0,015 ~dl/g. The
- , acetaldehyde content was 0.67 ppm.
Example 4
The following table reports the extrusion blow
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WO92/17519 PCT/E~2/00669
.
- .
2~S~, 9 lo
mouldinq conditions and the apparatus used for the produc-
tion of the bottles up to 1500 ml:
mould: rotative distributor ~ 2 moulds
head: PET covered mono parison
screw length: 24 L/D
screw size: 65 mm
screw type: standard PVC
article: round bottle
volume: up to lS00 ml
output: 50.4 Kg/h (depends on the bottle
volume)
parison length: up to 40 cm
production: 960 bottles/hour
cycle: 8.0 seconds
temperature
barrel: 250-C
profile head: 280C
die: 290C
The COPET was dried to a content of water less than
0.005% using dried air with Dew point between - 30C and
- 40-C.
The following table gives the blowing conditions and
the results obtained using the COPET of example l.
RESIN I BMREL / HE~D / DIE I BOTTLE / HOURS I BOTTLE I OUTPUT I ~RE~ CA I DRDP
TEllP. ¦ I IlElGHT I I SPEED I I TEST
'C I No. I gr I Kg~h I rp~ I ppD I Cl~
-I - I t
I COPET I 2~0 270 280 ~6Q I 42 1 1 1 50.4 1 48 1 ~-6 1 62 I
I~
:- ACA - acetaldehyde
xamPle 5 - - - ~ -
This example describes the extrusion blowing of COPET
produced accordinq to example and mixed before blowing
with polybutylenterephthalate (General Electric) (PBT); IV
WO92/17519 PCT/Er~2/00669
~ ~ 5~?~ 79
11
= 1.220 dl/g in amount of 3,5% by weight.
This mixture was dried and blowed according to the
general description of example 4.
The following table gives the blowing conditions and
the results obtained.
r I -- I I , I ,
RESINI BARREL / HE~D / DIE I BOTTLE ! HOURS I BOTTLE I OUTPUT I SCRE~ I ~C~ I DROP
TEllP. I I ~IEIG~IT I I SPEED I I TES~ I
C I No. j gr I gg/h I rp~ I pp~ I C~ ¦ :
COPET ~ 240 280 ~QO 960 1 42 1 1 1 50.4 ~ 1 3-7 1 70 1 -
Example 6
This example describes the extrusion blowing of COPET
of example 1 and mixed before blowing with 5% by weight of
polycarbonate (Dow Chem.).
This mixture was then dried and blowed according to
the general description of example 4.
The following table reports the conditions and the
obtained results.
~ES~N I B~RREL / HE~D / DIE I BOTTLE ~ HWRS I BOTTLE I OUTPUT I SCRE~ I DROP
TE11P, I I ~IEIGHT I I SPED I I TESI I ~
'C ¦ No. I gr I Kg/~ I rp~ I pp- I c~ I :
+ I 1- t - I 1~
I C~PET I 240 290 ~00 9~0 1 42 1 1 1 50.4 1 52 1 3-7 1 70 1
- L I ~ -- ! L
Example .7
This example describes the extrusion blowing of COPET
of example 1 mixed before blowing with 5~ by~weight of
phenoxy resin (Union Carbide).
This mixture was dried and blowed according to the
general description of example 4.
The following table reports the conditions and the
results obtained.
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wo 92/17~19 ~3 3~, 9 PCT/EP92/00669
12
I
F~ESlN I B~RREL / HEAD i DIE I EOTTLE; HOURS I BOTTLE I OUTPUT I SCRE~ Cn I SROP
TEHP. ¦ I liEIGHT I I SPEED I I TEST
~C I No. I gr I l~g/h I rp~i I pp9 I C~
t
I C~PET I 240 2B0 300 960 1 42 1 .1 150-4 1 50 1 5.1 1 6q 1
L I I I I _ ~ I I I
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