|||||||||||||||III US0051663 OA

United States Patent (19) 11) Patent Number: 5,166,310

Rooney (45) Date of Patent: Nov. 24, 1992
(54) PREPARATION OF POLYESTERS WITHTIN 3,716,523 2/1973 Cook ................................... 528/283
CATALYST 4,018,708 4/1977 Vogt et al. .......................... 252/431
4,020,010 4/1977 Vogt et al. .......................... 252/431
75 Inventor: Peter C. Rooney, Lake Jackson, Tex. 4,072,631 2/1978 Vogt et al. .......... ... 252/431
w 4,554,344 11/1985 Jackson, Jr. et al. ... 528/283
73) Assignee: Shetical Company, 4,970,288 11/1990 Larkin et al., ....................... 528/272
Primary Examiner-John Kight, III
(21) Appl. No.: 750,672 Assistant Examiner-T. Mosley
22 Filed: Aug. 27, 1991 (57) ABSTRACT
5
51) Int. Cl. ...................... C08G 63/78; 3, (5. Polyesters are prepared from dihydroxyl-containing
52 U.S. Cl. ....................... 528/283; 528/176: compounds and di-carboxylic acids or anhydrides or
e 8 o O O do no O D he d 4 528/193. 528/194. 528 /276 lower alkyl esters thereof in the presence of a combina
58) Field of Search ............... 528776,193.6.279, tion of tin catalysts comprising (1) at least one organotin
528/283 salt of a carboxylic acid, and (2) either (a) at least one
organotin oxide, or (b) at least one organostannoic acid,
(56) References Cited or (c) a combination of (a) and (b). The polyesters pre
U.S. PATENT DOCUMENTS pared by this process are useful in coating, adhesive,
2,720,507 10/1955 Caldwell ............................. 52.8/8 fiber and molding applications.
3,162,616 12/1964 Dombrow .. ... 528/283
3,345,339 10/1967 Parket et al. - - - - - - - - - - - - - - - - - - - - - - - - 528/283 3 Claims, No Drawings
 5,166,310
1. 2
polyesters can also be thinned in a suitable reactive
PREPARATION OF POLYESTERS WITH TIN monomer such as styrene or divinyl benzene as dis
CATALYST closed in the above references, or mixtures thereof and
the like.
FIELD OF THE INVENTION 5 It would be desirable to have available a process for
The present invention pertains to a process for the the preparation of polyesters which would result in less
preparation of polyesters in the presence of a combina reaction time and which would result in a polyester
tion of tin catalysts. with improved properties such as, lower color values,
BACKGROUND OF THE INVENTION 10 reduced by-products and the like.
It is well known that organotin compositions, includ SUMMARY OF THE INVENTION
ing organotin oxides, hydroxides, alkoxides and carbox The present invention pertains to an improved pro
ylates are effective as catalysts in the manufacture of cess for the preparation of hydroxyl or acid terminated
polyester resins and polyester-containing compositions. polyesters by reacting a dihydroxyl-containing com
The use of tin catalysts in the esterification of polyesters pound with a dicarboxyl-containing compound or an
is disclosed by Caldwell in U.S. Pat. No. 2,720,507, by hydride or lower alkyl ester thereof and optionally a tri
Dombrow et al. in U.S. Pat. No. 3,162,616, by Allisonet or poly-functional hydroxyl or carboxyl containing
al. in U.S. Pat. No. 3,345,339, by Cook in U.S. Pat. No. compound or anhydride or lower alkyl ester thereof in
3,716,523 and by Jackson, Jr. et al. in U.S. Pat. No.
4,554,334. The organotin catalysts decrease the time 20 the presence of a tin catalyst; wherein the improvement
required to complete the reaction. The use of non-toxic resides in conducting the reaction in the presence of a
organotin esterification catalysts in the production of combination of catalysts comprising (1) at least one
polyesters to produce non-toxic compositions is dis organotin salt of a carboxylic acid, and (2) either (a) at
cussed by Larkin et al. in U.S. Pat. No. 4,970,288. least one organotin oxide, or (b) at least one organostan
Polyesters are formed by the condensation of a diba- 25 noic acid, or (c) a combination of (a) and (b).
sic or polybasic acid and a dihydric or polyhydric alco The process of the present invention provides a faster
hol to form a series of ester linkages. Optionally, a tri reaction than does either of the catalyst components
functional or polyfunctional alcohol or acid functional employed alone and/or it provides a polyester product.
branching agent may be used to enhance the properties which has an improvement in one or more of the prop
of the polyester or polyester-containing material 30 erties selected from color, by-product formation or the
formed from the polyester. Also, optionally, monofunc like.
tional monomers such as benzoic acid or stearic acid can
be used to control molecular weight. DETAILED DESCRIPTION OF THE
Theoretically, one equivalent of polyol is utilized for INVENTION
each equivalent of acid. However, a hydroxyl-ter- 35 The process of the present invention can be con
minated polyester is prepared using an excess of polyol ducted at temperatures usually employed in the prepa
and a carboxyl-terminated polyester is prepared using
an excess of acid. When a carboxyl-perminated polyes ration of polyester resins, of from about 150 C. to about
ter is prepared in a two-stage or multi-stage reaction, it 270° C., preferably from about 170° C. to about 270° C.,
is common to use excess polyol in the first stage and 40 more preferably from about 180° C. to about 250 C.
react this hydroxyl-terminated polyester with an excess The reaction is conducted for a time sufficient to bring
amount of acid or anhydride in the second stage. The the reaction to the desired degree of completion. For
advantage of a two-stage synthesis, as disclosed in the hydroxyl terminated polyesters, the reaction is usually
above patents, is that the polyester can be prepared considered complete when the hydroxyl value of the
having excellent color and/or can be produced in less 45 reaction mixture is below about 150, preferably below
time than by using a one-stage reaction. about 100, more preferably below about 80. For acid or
Esters can also be prepared by transesterification carboxyl terminated polyesters, the reaction is usually
reactions. When using the ester-interchange method the considered complete when the acid number of the reac
long chain in the polyester is built up by a series of ester tion mixture is below about 100, preferably below about
interchange reactions wherein the glycol displaces an 50 90, more preferably below about 70.
ester to form the glycolester. Included are the reactions At temperatures below about 150° C. the reaction
between two esters to yield two new esters and also generally proceeds too slow to suit industrial needs.
include the transesterification reactions where the con
ponents of the esters involved are polyhydroxy alcohols At temperatures above about 270° C. the polyester
and polybasic acids. 55 may become colored and/or by-product formation such
As discussed in the above patents, the polyester is as The ethers may result.
reaction is conveniently conducted at pressures
prepared by heating the condensing mixture at tempera
tures of at least about 170° C. up to about 275 C. or from about 700 mm Hg to about 1,500 mm Hg. The
higher in order to maintain the fluid state. The reaction reaction temperature and pressure are balanced such
can be performed above atmospheric pressure, up to 60 that the water or low-boiling alcohol of reaction is
about 20 psig (14062 kg/m2) or higher, at atmospheric removed as quickly as possible while not distilling the
pressure or under vacuum to about 15 mm Hg or lower. low-boiling reactants, generally glycols, from the reac
The esterification reaction can be conducted in the tion. It is generally advantageous to finish the reaction
presence of a suitable solvent such as toluene or xylene at reduced pressure, generally below about 100 mm Hg,
and the like. Nitrogen, argon, helium or any other suit- 65 preferably below about 50 mm Hg, more preferably
able gas may be introduced into the reactor to keep air below about 10 mm Hg.
out of the reactor or to facilitate the removal of water, Pressures below about 10 mm Hg are generally diffi
low-boiling alcohol, mixtures thereof or the like. The cult to achieve on an industrial scale.
 5,166,310
3 4.
At pressures above about 1500 mm Hg, the rate of
removal of water or low-boiling alcohol from the reac
tion is greatly reduced.
The reaction temperature and pressure are balanced
such that the water or low-boiling alcohol produced in
the reaction, depending upon whether the starting ma
terial is an acid or a lower alkyl ester thereof, is re
moved as quickly as possible while not distilling off any
low-boiling reactants.
The time required to achieve the desired degree of
reaction depends upon many factors, such as heating
and cooling capacity, reaction vessel size, particular
reactants and catalyst, and the like. Generally, for lab
scale reactions up to about 2 liters, the reaction is usu
ally complete in less than about 12 hours, preferably in
less than about 10 hours, more preferably in less than
about 8 hours.
It is anticipated that in most commercial production
reactors used on an industrial scale, the time to essen
tially complete the reaction is less than about 36 hours,
preferably less than about 30 hours, more preferably less
than about 24 hours.
ORGANOTIN SALTS
Suitable organotin salts of a carboxylic acid which
can be employed herein include, for example, those
represented by the following formulas R-Sn(O2CR"),
R2Sn(OR")2, R2Sn(O2CR")(OCR"), R-Sn(O2CR")3 or
R-Sn(O2CR")2Y; wherein each R is the same or differ
ent and is an alkyl group having from 1 to about 20,
preferably from 1 to about 12, more preferably from 1
to about 8, carbon atoms, or an aryl, alkaryl or cycloal
kyl group having from about 6 to about 14 carbon
atoms; each R' can be the same or different and is an
alkyl group having from 1 to about 20, preferably from
1 to about 12, more preferably from 1 to about 8, carbon
atoms, or an aryl, alkaryl or cycloalkyl group having
from about 6 to about 14 carbon atoms. The R groups
can be saturated or unsaturated and can be substituted
or unsubstituted with such substituent groups as alkyl,
aryl or cycloalkyl groups having from 1 to about 20
carbon atoms, halogen, preferably chlorine or bromine,
-NO2, and the like; and Y is a halogen, preferably
chlorine or bromine. Such organotin salts of a carbox
ylic acid include, but are not limited to stannous acetate,
stannous laurate, stannous octoate, stannous oleate,
stannous oxalate, dibenzyltin diacetate, dibenzyltin dis
tearate, dibutylmethoxytin acetate, dibutyltin diacetate,
- dibutyltin dilaurate, dibutyltin maleate, dilaurytin diac
etate, dioctyltin diacetate, dioctyltin dilaurate, diphe
nyltin diacetate, methyltin trilaurate, methyltin tris(2-
ethylhexoate), butyltin triacetate, butyltin trilaurate,
butyltin tris(2-ethylhexoate), or any combination
thereof and the like. Particularly suitable such organo
tin salts of carboxylic acids include, for example, dibu
tyltin diacetate, dibutyltin dilaurate, stannous octoate,
dioctyltin dilaurate or any combination thereof and the
like.
ORGANOTIN OXDES
Suitable organotin oxides which can be employed
herein include, for example, those represented by the
formula R2SnO wherein R is as defined above. Such
organotin oxides include, but are not limited to bis(car
bomethoxyethyl) tin oxide, diallyltin oxide, dibenzyltin
oxide, dibutyltin oxide, dicyclohexyltin oxide, dilauryl
tin oxide, dimethyltin oxide, di-1-naphthyltin oxide,
dioctyltin oxide, diphenyltin oxide, divinyltin oxide, or
any combination thereof and the like. Particularly suit
able organotin oxides include, for example, dibutyltin
oxide, dimethyltin oxide or any combination thereof
and the like.
5
ORGANOSTANNOIC ACIDS
Suitable organostannoic acids which can be en
ployed herein include, for example, those represented
by the formula R-SnOOH or their corresponding anhy
10 drides represented by the formula (R-SnO)2O wherein
R is as defined above. Such organostannoic acids or
anhydrides thereof include, but are not limited to phe
nylstannoic acid, chlorobenzylstannoic acid, 1-dodecyl
stannoic acid, methylstannoic acid, 1-naphthylstannoic
15 acid, butylstannoic acid, octylstannoic acid, their anhy
drides, or any combination thereof and the like. Particu
larly suitable organostannoic acids or anhydrides in
clude, for example, butylstannoic acid, methylstannoic
acid or any combination thereof and the like.
CATALYST CONCENTRATION
The tin catalysts of the present invention are em
ployed in an amount which provides a total amount of
catalyst of from about 0.001 to about 3, preferably from
25 about 0.01 to about 1.0, more preferably from about 0.05
to about 0.2 weight percent based upon the weight of
the reactants.
The organotin salt of a carboxylic acid catalyst (com
ponent 1) is employed in an amount of from about 0.01
to about 99.99, preferably from about 0.01 to about 60,
more preferably from about 0.01 to about 30 mole per
cent based upon the total amount of catalyst; and the
organotin oxide and/or organostannoic acid catalyst
(component 2) is employed in an amount of from about
35 0.01 to about 99.99, preferably from about 50 to about
99.99, more preferably from about 70 to about 99.99
mole percent based upon the total amount of catalyst.
DIOL COMPOUNDS
Suitable diols (compounds containing two hydroxyl
groups per molecule) which can be employed herein,
include, for example, aliphatic, cycloaliphatic or aro
matic diols which can be either saturated or unsatu
rated. These diols can have from 2 to about 20, prefera
45 bly from about 2 to about 12, more preferably from 2 to
about 8, carbon atoms per molecule. Such diols include,
but are not limited to, ethylene glycol, propylene gly
col, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, pen
tanediol, hexanediol, heptanediol, neopentyl glycol,
nonanediol, decanediol, 2,2,4-trimethyl-1,3-pentanediol,
diethylene glycol, dipropylene glycol, cyclohex
anedimethanol, 2-methyl-1,3-propanediolor any combi
nation thereof and the like. Particularly suitable such
diols include, for example, neopentyl glycol, ethylene
55 glycol, cyclohexanedimethanol or any combination
thereof and the like.
ORGANIC DICARBOXYLIC ACDS and
ANHYDRIDES and ESTERS
Suitable organic dicarboxylic acids which can be
employed herein include, for example, aliphatic, cyclo
aliphatic. or aromatic diacids having from about 2 to
about 20 carbon atoms. These diacids can be either
saturated or unsaturated. Also suitable are the anhy
65 drides thereof. Such diacids or anhydrides include, but
are not limited to, adipic acid, terephthalic acid, oxalic
acid, succinic acid, sebacic acid, fumaric acid, azelaic
acid, suberic acid, phthalic acid, isophthalic acid, hexa
 5,166,310
5 6
hydrophthalic acid, succinic anhydride, phthalic anhy inlet (initially set at 5 ml/min) and connected to an oil
dride or any combination thereof and the like. Particu heated column (maintained at 100° C.) packed with
larly suitable such acids or anhydrides include, for ex stainless steel wire. This oil heated column is connected
ample, terephthalic acid, isophthalic acid, adipic acid or to a Dean-Stark trap equipped with a condenser for the
any combination thereof and the like. 5 collection of water.
Also suitable are the lower alkyl, C to C4 esters of The polyesters are prepared in two steps or stages as
any of the aforementioned dicarboxylic acids. Particu follows:
larly suitable such esters include, for example, the
methyl, ethyl or propyl mono and diesters of adipic Stage 1-Preparation of a Hydroxyl-terminated
acid, terephthalic acid, oxalic acid, succinic acid, seba 10 Polyester
cic acid, fumaric acid, azelaic acid, suberic acid, The flask is charged with the following:
phthalic acid, isophthalic acid, hexahydrophthalic acid,
or any combination thereof and the like.
Terephthalic acid 867.3 g (5.1 moles)
MONOFUNCTIONAL REACTANTS Neopenty glycol 5700 g (5.5 notes)
15
In some instances, it is desirable to incorporate mono Trimethylolpropane 10.7 g (0.1 mole)
Tin catalyst 4.76 innoles total
functional compounds into the reaction to control mo
lecular weight. Suitable such monofunctional reactants
include, for example, benzoic acid, tert-butylbenzoic This mixture is heated to 180 C. and held at that ten
acid, phenylbenzoic acid, stearic acid, tert-butylphenol, 20 perature for 30 min. The temperature is then increased
benzyl alcohol, or any combination thereof and the like. to 200 C. for a total of 30 min., then to 220 C. for a
These monofunctional compounds, when employed, total of 2 hrs, then to 230 C. for a total of 1 hr and
are employed in amounts of from about 0.01 to about 10, finally to 250° C. The reaction is monitored by periodi
preferably from about 1 to about 8, more preferably cally measuring the acid number and the viscosity using
from about 2 to about 5 weight percent based upon the 25 an I.C.I. cone and plate viscometer. When a viscosity of
total weight of reactants. about 50 Poise at 175 C. and an acid number of about
POLYFUNCTIONAL REACTANTS 14 is obtained the resin is clear and the first stage is
completed. The hydroxyl number of this polyester is
In some instances it is desirable to introduce chain calculated to be about 58 at this stage.
branching into the polyester being prepared. In order to 30
do this a tri- or poly-functional reactant is introduced Stage 2-Preparation of a Carboxyl-Terminated
into the reaction mixture. This tri- or poly-functional Polyester
reactant can be either hydroxyl or acid or anhydride To the reactor containing the reaction product from
functional. Particularly suitable tri- or poly-functional Stage 2 is added:
reactants which can be employed herein include, for 35
example, trimellitic anhydride, trimethylolpropane,
glycerine, triethylolpropane and pentaerythritol or any Isophthalic acid 126.6 g. (0.8 mole)
combination thereof and the like.
These polyfunctional compounds are employed in On hour after addition of the isophthalic acid the nitro
amounts of from about 0.01 to about 10, preferably from 40 gen flow rate is increased to 10 ml/min. Forty-five
about 0.1 to about 7, more preferably from about 0.1 to minutes later the nitrogen flow rate is increased to 20
about 5 weight percent based upon the total weight of ml/min until a final acid number of about 38 and a final
reactartS.
viscosity of about 190 Poise at 175 C. is obtained
REACTION SOLVENTS whereupon the resin is poured onto a pan of aluminum
45 foil. The APHA color of all the resins in this example,
If desired, the process of the present invention for measured as a 10 wt % solution of resin in tetrahydrofu
preparing polyesters can be conducted in the presence ran, are less than or equal to about 20.
of a suitable solvent such as, for example, aromatic The results are given in Table I.
hydrocarbons, ethers, sulfones, chlorinated aromatic
hydrocarbons, sulfolanes, sulfoxides or any combina 50 TABLE 1
tion thereof and the like. Particularly suitable such sol Tine to Tine to
vents include, for example, toluene, xylene, diphenyl 1st Stage Final Acid
ether, dimethyl sulfolane or any combination thereof Catalyst (min) Number(min)
and the like. 1. Butylstannoic acid 45 635
2 Dimethyltin oxide 400 630
The solvent can be employed in amounts of from 55 3. Dibutyltin oxide 475 655
about 40 to about 95, preferably from about 45 to about 4 Dioctyltin oxide 475 670
90, more preferably from about 50 to about 90, percent 5 Dibutyltin diacetate 500 >635
by weight based upon the weight of the reactants. 6 Dibutyltin dilaurate
7 Stannous octoate
470
>690 >690
695
The polyesters prepared by the process of the present 8 Butylchlorotin dihydroxide 425 670
invention are useful in coating, adhesive, fiber and 60 9 Butylchlorotin dihydroxide/ 450 720
molding applications. Dibutyltin dilaurate
The following examples are illustrative of the inven 10 Butylstannoic acid/dibutyltin
diacetate
420 600
tion. 1 Butylstannoic acid/dibutyltin 360 495
EXAMPLES 1-7 dilaurate
65 12. Butylstannoic acid/stannous 455b 590
Apparatus octoate
13 Dibutyltin oxide/dibutyltin 450 620
These examples are conducted in a 2-L flask equipped diacetate
with a heating mantle, stirrer, thermometer, nitrogen 14 Dibutyltin oxide/dibutyltin 415 65
 5,166,310
7 8
TABLE 1-continued finally to 240° C. The reaction is monitored by periodi
Time to Time to
cally measuring the acid number and the viscosity using
1st Stage Final Acid an I.C.I. cone and plate viscometer. When a viscosity of
Catalyst (min) Number(min) about 10 Poise at 175 C. and an acid number of about
dilaurate 5 10 is obtained the resin is clear and the first stage is
15 Dibutyltin oxide/stannous 410 575 completed. The hydroxyl number of this polyester is
octoate calculated to be about 87 at this stage.
16 Dimethyltin oxide/dibutyltin 420 600
dilaurate
17 Dioctyltin oxide/dibutyltin 420 550
Stage 2-Preparation of a Carboxyl-Terminated
dilautate 10 Polyester
Not an example of the present invention. To the reactor is added:
is not faster than single catalyst, however, at a different catalyst mole ratio, the
reaction is faster than single catalyst (see Example 18).
is not faster at the first stage than a single catalyst, but like above, a different Isophthalic acid 239.9 g
catalyst ratio should be faster than a single catalyst. (1.4 moles)
Moleratio is 50/50. 15

One hour after addition of the isophthalic acid the

EXAMPLE 8 nitrogen flow rate is increased to 10 ml/min. The resin
The polyester prepared in Example 10 (above) is is poured onto a pan of aluminum foil after a total syn
prepared here exactly as above using a different mole 20
thesis time of 490 minutes whereupon the final acid
ratio of butylstannoic acid to dibutyltin diacetate. When number and viscosity is recorded. The results show that
an equimolar amount of these two catalysts is used as in the synthesis times to the end of the first stage are
Example 10 above, the time to complete the first stage shorter for the combination tin catalyst and that the
(420 min) is not faster than butylstannoic acid alone (415 final acid number at 490 min total synthesis time is
min). In this Example 18, 0.80 g butylstannoic acid (3.83 25
lower for the catalyst combination than for the individ
mmoles) and 0.32 g dibutyltin diacetate (0.91 nmoles) ual catalyst DBTO or DBTDA. The results are given in
are used. The time to complete the first stage is 360 min Table II.
and the time to reach the final acid number of about 38 TABLE II
is 525 min. The APHA color of the final resin is 10. This Catalyst Time to Final Acid
example demonstrates the synergy of the two catalysts 30 Catalyst Mole ratio list State(min) Number
versus the use of only one catalyst at a substantially 19 DBTOa 400 128
equimolar concentration (4.76 mmoles for the single 20 DBTDA re 390 98
catalysts vs. 4.74 mmoles for the combination catalyst). 21 dBTO/OBTDA 0.3 370 90
Further, it demonstrates that an equimolar concentra 22
23
DBTO/DBTDA
DBTO/DBTDA
0.25
0.50
355
370
88
89
tion of catalyst combination may not be the optimum 35 24 DBTO/DBTDA 0.94 340 87
for a particular polyesterification reaction.
"Not an example of the present invention.
EXAMPLES 19-24 DBTO is dibutyltin oxide.
DBTDA is dibutyltin diacetate.
A relatively high acid number polyester is prepared
in a two-stage process using various mole ratios of dibu EXAMPLES 25-27
tyltin oxide (DBTO) and/or dibutyltin diacetate
(DBTDA) catalyst. A total of 4.76 mmoles of tin cata Preparation of an Acid-Terminated Polyester in One
lyst is used in all reactions. Stage
Apparatus Apparatus
4
These examples are conducted in a 2-L flask equipped 5 The following examples are conducted in a 2-L flask
with a heating mantle, stirrer, thermometer, nitrogen equipped with a heating mantle, stirrer, thermometer,
inlet (initially set at 5 ml/min) and connected to an oil nitrogen inlet (initially set at 5 ml/min) and connected
heated column (maintained at 100° C.) packed with to an oil heated column (maintained at 100 C.) packed
stainless steel wire. This oil heated column is connected 50 with stainless steel wire. This oil heated column is con
to a Dean-Stark trap equipped with a condenser for the nected to a Dean-Stark trap equipped with a condenser
collection of water. for the collection of water.
The polyesters are prepared in two steps or stages as A carboxyl-terminated polyester is prepared in one
follows: stage. A total of 8.03 mmoles of tin catalyst is used in all
Stage 1-Preparation of a Hydroxyl-terminated 55 reactions. When two catalysts are used, equimolar
amounts of each catalyst are used for a total of 8.03
Polyester nmoles.
The flask is charged with the following: The flask is charged with the following:
Terephthalic acid 441.6 g (2.7 moles) Terephthalic acid 762.6 g (4.6 moles)
Neopentylglycol 454.1 g (4.4 moles) Neopentyl glycol 607.0 g (5.8 moles)
Adipic acid 156.0 g (1.1 moles) 1,4-cyclohexanedicarboxylic acid 225.0 g (.3 moles)
Tin catalyst (4.76 mmoles total) Trimellitic anhydride 16.1 g (0.1 moles)
Tin catalyst 8.03 nmoles total
This mixture is heated to 180 C. and held at that 65
temperature for 30 min. The temperature is then in This mixture is heated to 180 C. and held at that
creased to 200 C. for a total of 30 min., then to 220 C. temperature for 30 min. The temperature is then in
for a total of 2 hrs, then to 230' C. for a total of 1 hr and creased to 200 C. for a total of 30 min., then to 220 C.
 5,166,310
9 10
in the presence of a tin catalyst; the improvement com
for a total of 1.5 hrs, then to 230 C. for a total of 1 hr,
then to 240° C. for a total of 1.5 hrs and finally to 250 prises conducting the reaction in the presence of a syn
C. For each reaction, the nitrogen flow rate is increased ergistic combination of catalysts consisting of (1) at least
to 10 ml/min when the reaction time reached 405 min. one organotin salt of a carboxylic acid, and (2) either (a)
The acid number (AN) and viscosity (I.C.I. cone and 5 at least one organotin oxide, or (b) at least one organos
plate at 150° C.) of the resin is measured at 405 min and
465 min total reaction time. The results are given in the tannoic
2. The
acid, or (c) a combination of (a) and (b).
process of claim 1 wherein
following Table III. (a) the reaction temperature is from about 150° C. to
TABLE III O about 270° C.;
Viscos- Viscos (b) the dihydroxy-containing compound is an ali
AN at ity at AN at ity at phatic, cycloaliphatic or aromatic hydroxyl-con
Catalyst 405 Inin 405 min 465 min 465 min
taining compound; and
25" Dibutyltin oxide 62 56 48 108 (c) the dicarboxylic acid is an aliphatic, cycloali
26 Dioctyltin 59 62 45 128
dilaurate 5 phatic or aromatic carboxyl-containing compound
27 Dibutyltin
oxide/dioctyltin
51 72 39 44 or an anhydride or lower alkyl ester thereof.
dilaurate 3. The process of claim 1 wherein
Not an example of the present invention. (a) the reaction temperature is from about 180° C. to
about 250 C.;
What is claimed is:
20 (b) the dihydroxyl-containing compound is neopentyl
1. In a process for the preparation of hydroxyl or acid glycol, ethylene glycol, cyclohexanedimethanol or
terminated polyesters by reacting a dihydroxyl-contain any combination thereof; and
ing compound with a dicarboxyl-containing compound (c) the dicarboxylic acid is terephthalic acid, iso
or anhydride or lower alkyl ester thereof and optionally phthalic acid, adipic acid or any combination
a tri- or poly-functional hydroxyl or carboxyl contain thereof,
ing compound or anhydride or lower alkyl ester thereof k Sk k k

30

35

40

45

50

55

60

65
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 5,166,310
DATED November 24, 1992
INVENTOR(S) : Peter C. Rooney
It is certified that error appears in the above-identified patent and that said Letters Patent is hereby
corrected as shown below: P

Column 10, line 1-2, "comprises" should be --consisting of-.

Signed and Sealed this

Thirtieth Day of November, 1993

At est 6. team
BRUCELEMAN

Attesting Officer Corrissioner of Pateries and Trademarks