O

||||||||||||||||| US005369210A
United States Patent (19) 11 Patent Number: 5,369,210
George et al. 45 Date of Patent: Nov. 29, 1994
54. HEAT-RESISTANT WATER-DISPERSIBLE 3,436,376 4/1969 Puling et al. ....... ... 528/298
SULFOPOLYESTER COMPOSITIONS y
: 2. g E. et al.
y elberger e - -- - -
7.
75 Inventors: Scott E. George; Bobby J. Sublett, 3,734,874 5/1973 Kibler et al. ........ ... 524/603
both of Kingsport, Tenn. 3,779,993 12/1973 Kibler et al..... ... 528/288
73) Assignee: Eastman Chemical Company 4,480,085 10/1984 Larson et al. ....................... 528/295
Kingsport, Tenn. Primary Examiner-Samuel A. Acquah.
21) Appl. No.: 95,464 we 1 Y9
Attorney, Agent, or Firm-John D. Thallemer
22 Filed: Jul. 23, 1993 (57) ABSTRACT
s The present invention relates to sulfonate containing
: s: Ogil OMV8 V/Aids e sa s a oss oo e o e o os e a a a so 9 s
water-dispersible or water-dissipatible sulfopolyester
528/275; 528/286; 528/295; 528/298; 528/302. compositions. The sulfopolyesters utilize at least two
528/307. 528/308. 528/308.6 524/602. dicarboxylic acids, one of which is a naphthalene dicar
524/603; 524/706; 524/711; 524/773; 524/777; boxylic acid. This combination of dicarboxylic acids
524/787 allows for the sulfopolyesters to maintain glass transi
58) Field of Search ............... 528/290, 295, 272,275, tion temperatures (Tg) of greater than 89 C. and exhibit
528/286, 293,295, 298,302, 307, 308,308.6; lower melt viscosities than sulfopolyesters containing
524/602, 603, 706, 711, 773, 777, 787 all naphthalenediyl units or all isophthtaloyl units. The
sulfopolyesters of this invention are useful in applica
(56) References Cited tions where improved heat and blocking resistance is
U.S. PATENT DOCUMENTS required.
3,018,272 1/1962 Griffing et al. ..................... 528/293
3,123,587 3/1964 Hogsed et al. ...................... 528/293 12 Claims, No Drawings
 5,369,210
1. 2
high melt viscosities resulting in manufacturing prob
HEAT-RESISTANT WATER-OSPERSIBLE lems.
SULFOPOLYESTER COMPOSITIONS Water-dispersible sulfopolyesters containing only
isophthalate acid units or only terephthalic acid units
FIELD OF THE INVENTION tend to have Tg's less than 89 C. with aliphatic and
The present invention relates to sulfonate containing alicyclic diols, while analogous systems containing only
water-dispersible or water-dissipatible sulfopolyester naphthalenedicarboxylic acid units tend to have a maxi
compositions. The sulfopolyesters utilize at least two mum Tg around 130 C., when common aliphatic and
dicarboxylic acids, one of which is a naphthalenedicar cycloaliphatic diols are used. Unexpectedly, the present
boxylic acid. This combination of dicarboxylic acids
0. inventors have determined that sulfopolyesters based on
allows for the sulfopolyesters to maintain glass transi isophthalate or terephthalate units modified with naph
tion temperatures (Tg) of greater than 89° C. and exhibit thalene units not only maintain Tg's in the 89 C. to 130
lower melt viscosities than sulfopolyesters containing C. range, but also exhibit melt viscosities lower than
comparable systems containing only isophthalic acid or
all naphthalenediyl units or all isophthtaloyl units. The 15 only naphthalene dicarboxylate units. It is desirable to
sulfopolyesters of this invention are useful in applica have lower melt viscosities, since production process
tions where improved heat and blocking resistance is equipment is limited to a certain melt viscosity. Thus,
required. lower melt viscosities will allow for higher molecular
BACKGROUND OF THE INVENTION weights to be obtained for a given sulfopolyester.
20
Poly(ethylene-2,6-naphthalene dicarboxylate), re SUMMARY OF THE INVENTION
ferred to as PEN, has been used in films, fibers, and Accordingly, it is one object of the present invention
molded objects. U.S. Pat. Nos. 3,546,008, 3,563,942, to provide water-dispersible high molecular weight
3,734,874, and 3,779,993 disclose water-dispersible co sulfopolyester compositions.
polyester and polyesteramide compositions containing 25 Accordingly, it is another object of the invention to
metal sulfonate groups. None of the references, how provide water-dispersible sulfopolyesters which have a
ever, use Poly(ethylene-2,6-naphthalene dicarboxylate) Tg of greater than 89 C. and which exhibit lower melt
or mention Tg. U.S. Pat. No. 4,480,085 discloses com viscosities.
positions containing 1,8-naphthalene dicarboxylic acid Still another object of the invention is to provide
and sodiosulfoisophthalic acid as the dicarboxylic acid 30 water-dispersible sulfopolyester compositions which
component in combination with ethylene glycol. The are useful in applications where increased abrasion re
sulfopolyester had a Tg of 73 C. In contrast, the pres sistance, inherent higher process temperature condi
ent inventors have determined that only certain naph tions, and improved blocking resistance are required.
thalenediyl isomers will yield polymers with Tg values These and other objects are accomplished herein by a
above 89 C. 35 water-dispersible sulfopolyester having a Tg of greater
U.S. Pat. No. 3,436,376, discloses polyesters synthe than 89 C. and low melt viscosity consisting essentially
sized from 2,6-naphthalenedicarboxylic acid, and ethyl of repeat units from:
ene glycol. The polyesters have Tg's of approximately (a) 10 to 93 mole percent of a dicarboxylic acid se
125 C. Tg values of 88 C. and 73° C. were reported for lected from the group consisting of naphthalene
the analogs where the ethylene glycol was replaced 2,6-dicarboxylic acid, naphthalene-2,7-dicarboxy
with 1,2-propane diol and 1,3-propane diol, respec lic acid, naphthalene-2,6-dicarboxylate ester and
tively. The polyesters of U.S. Pat. No. 3,436,376 did not naphthalene-2,7-dicarboxylate ester;
contain any sulfomonomer and were not water-dispersi (b) 2 to 85 mole percent of a dicarboxylic acid se
ble or water-dissipatible. lected from the group consisting of aromatic dicar
U.S. Pat. No. 3,123,587, discloses compositions
45 boxylic acids, saturated aliphatic dicarboxylic
which are resistant to hydrolysis compared to 5-sul acids, cycloaliphatic dicarboxylic acids, and com
foisophthalic acid modified poly(ethylene terephthal binations thereof;
ate) derived fibers. The compositions contain i to 5 (c) a diol; and
mole % of 5-sulfoisophthalic acid with 75 mole % of the 50 (d) a difunctional sulfomonomer containing at least
total acid component comprised of 2,6 or 2,7-naphtha one sulfonate group attached to an aromatic nu
lenediyl units and 75 mole % of the total glycol compo cleus wherein the functional groups are hydroxy,
nent comprised of cyclohexanedimethanol. Improved carboxy or amino, provided the difunctional sul
hydrolytic stability was touted as an attribute of the fomonomer is present in an amount from 5 to 40
mole percent based on 100 mole percent dicarbox
invention. Thus, the polyesters are less likely to be 55 ylic acid and 100 mole percent diol.
water dispersible.
Copending commonly assigned U.S. Pat. Application DESCRIPTION OF THE INVENTION
Ser. No. 08/041,105 abandoned discloses water-dispers This invention discloses compositions and methods of
ible sulfopolyesters having a Tg above 89 C. which preparation for linear, water-dispersible sulfopolyesters
contain a dicarboxylic acid component of poly(ethy 60 having a Tg value of at least 89 C. and a low melt
lene-2,6-naphthalene dicarboxylate and a sulfomo viscosity. The term “water-dispersible' is used inter
nomer, and a diol component containing at least 35 changeably with other descriptors such as "water-dis
mole percent of selected diols. The sulfopolyesters of sipatible”, “water-soluble” or “water-dispellable'. All
the copending application overcame the problems asso of these terms refer to the activity of water or a mixture
ciated with prior patents which taught that increasing 65 of water with a water-miscible organic solvent on the
the glass transition temperature of the polyesters re sulfopolyesters described herein. This terminology in
duces the water-dispersibility of the polyesters. The cludes conditions where the sulfopolyester is dissolved
copending application sulfopolyesters, however, posses to form a true solution or is dispersed within an aqueous
 5,369,210
3 4.
medium. Due to the statistical nature of polyester com of diols is stipulated only by the requirements that the
positions, it is possible to have soluble and dispersible final product possess a Tg equal to or greater than 89
fractions when a single polyester is acted upon by an C. while maintaining water-dispersibility.
aqueous medium. An aspect of the present invention concerns the effect
The sulfopolyester contains repeat units from at least 5 of diol chain length on the Tg of the resulting product.
two dicarboxylic acids, a diol, and a difunctional sul The structures: HO-CH2-(CH2)-OH and HO
fomonomer. At least one of the dicarboxylic acids, com (OCH2-CH2)-OH refer to the homologous series' of
ponent (a), is 10 to 93 mole percent based on 100 mole diols that are composed of methylene and oxyethylene
% dicarboxylic acid component, of naphthalene-2,6- subunits. Values of n for HO-CH2-(CH2)n-OH are
dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 10 normally in the range from 1 to 12. As n increases the
naphthalene-2,6-dicarboxylate ester, or naphthalene Tg for a resulting homopolyester resin is decreased
2,7-dicarboxylate ester. Preferably, the dimethyl ester accordingly. Therefore, modification of essentially a
forms are used. sulfonate-containing poly(ethylene naphthalene dicar
In addition to the 2,6- or 2,7-naphthalene dicarbox boxylate) requires proportionately smaller molar
ylic acid or 2,6- or 2,7-dicarboxylic ester, the dicarbox- 15 amounts of co-diol as n increases. A similar trend is
ylic acid component contains 2 to 85 mole percent of a observed when n increases from one (diethylene glycol)
dicarboxylic acid, component (b), which is selected to about for oxyethylene glycols.
from aliphatic, alicyclic, and aromatic dicarboxylic
acids. Examples of these dicarboxylic acids include as In the case of HO-(OCH2-CH2)-OH, referred to
malonic, dimethylmalonic, succinic, dodecanedioic, 20 10 poly(ethylene
to 5.0,
glycol) or PEG, the value of x will be
preferably about 20, which translates into a
glutaric, adipic, trimethyladipic, pimelic, 2,2-dimethyl PEG monomer molecular
glutaric, azelaic, sebacic, fumaric, suberic, maleic, ita ably about 1000. Typicallyweight less
of at least 500, prefer
than 5 mole percent of
conic, 1,3-cyclopentane dicarboxylic, 1,2-cyclohex PEG incorporation, based on total diol, will be used
anedicarboxylic, 1,3-cyclohexanedicarboxylic, 1,4- since a Tg of greater than 89 C. is required. One advan
cyclohexanedicarboxylic, phthalic, terephthalic, iso- 25
phthalic, 2,5-norbornanedicarboxylic, diphenic, 4,4'- tage of high molecular weight PEG modification is the
oxydibenzoic, diglycolic, thiodipropionic, 4,4'-sulfonyl ability to attain higher molecular weights without los
ing water-dispersibility. It is important to note that high
dibenzoic, 1,8-naphthalenedicarboxylic, and 2,5-naph sulfomonomer levels result in high process melt viscosi
thalenedicarboxylic. The anhydride, acid chloride, and
ester derivatives of the above acids may also be used. 30 ties which limit the molecular weight attainable in the
melt phase. A low molecular weight determined by an
The preferred dicarboxylic acid(s) to be used along inherent
with naphthalene dicarboxylic acid or naphthalene di may resultviscosity in poor
measurement of less than 0.1 dl/g
physical-properties such as low Tg
carboxylate ester are isophthalic acid, terephthalic acid, and inadequate tensile strength.
dimethyl terephthalate, and dimethyl isophthalate.
One aspect of this invention concerns the amount of 35 The difunctional sulfomonomer, component (d), of
2,6- or 2,7-naphthalenediyl modification necessary for a the sulfopolyester may be a dicarboxylic acid or an ester
given dicarboxylic acid or dicarboxylic acid combina thereof containing a metal sulfonate group (-SO3), a
tion to result in a polymer having a Tg above 89 C. In diol containing a metal sulfonate group, or a hydroxy
general, the amount of 2,6- or 2,7-naphthalenediyl mod acid containing a metal sulfonate group. Suitable metal
ification will decrease in the order: aliphatic > cycloali- 40 cations of the sulfonate salt may be Nat, Li, K,
phatic > aromatic. Increasing the chain length of an Mg++, Ca++, Ni++, Fe++, Fe+++, Zn- + and sub
aliphatic acid will result in a corresponding decrease in stituted ammonium. The term "substituted ammonium'
Tg, thus, requiring a higher level of naphthalenic modi refers to ammonium substituted with an alkyl or hy
fication. droxy alkyl radical having 1 to 4 carbon atoms. It is
The diol component, component (c), of the sul- 45 within the scope of this invention that the sulfonate salt
fopolyester consists of a diol selected from suitable is non-metallic and can be a nitrogenous base as de
aliphatic diols, cycloaliphatic diols, aromatic diols and scribed in U.S. Pat. No. 4,304,901 which is incorporated
combinations thereof. The aliphatic diols preferably herein by reference.
have 2 to 20 carbon atoms, and the cycloaliphatic diols The choice of cation will influence the water-dispers
preferably have 6 to 20 carbon atoms. The diol compo- 50 ibility of the resulting polyester. Monovalent alkali
nent may also include mixtures of diols. Included within metal ions yield polyesters that are less readily dissi
the class of aliphatic diols are aliphatic diols having pated by cold water and more readily dissipated by hot
ether linkages such as polydiols having 4 to 800 carbon water, while divalent and trivalent metal ions result in
atoms. Suitable diols include: ethylene glycol, diethyl polyesters that are not ordinarily easily dissipated by
ene glycol, triethylene glycol, 1,2-propanediol, 1,3- 55 cold water but are more readily dispersed in hot water.
propanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2,2- Depending on the end use of the polymer, either of the
dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3- different sets of properties may be desirable. It is possi
propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,4- ble to prepare the sulfopolyester using, for example, a
butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4- sodium sulfonate salt and later by ion-exchange replace
trimethyl-1,6-hexanediol, thioethanol, 1,2-cyclohex- 60 this ion with a different ion, for example, calcium, and
anedimethanol, 1,3-cyclohexanedimethanol, and 1,4- thus alter the characteristics of the polymer. In general,
cyclohexanedimethanol. Preferably, the diol(s) are eth this procedure is superior to preparing the polymer
ylene glycol, combinations of ethylene glycol with di with divalent salts inasmuch as the sodium salts are
ethylene glycol, combinations of diethylene glycol with usually more soluble in the polymer manufacturing
1,4-cyclohexanedimethanol, combinations of ethylene 65 components than are the divalent metal salts. Polymers
glycol with 1,4-cyclohexanedimethanol, and combina containing divalent and trivalent metal ions are nor
tions of ethylene glycol or diethylene glycol with a mally less elastic and rubber-like than polymers contain
variety of suitable co-diois. The particular combination ing monovalent ions.
 5,369,210
5 6
The difunctional sulfomonomer contains at least one of both stages are facilitated by appropriate catalysts
sulfonate group attached to an aromatic nucleus which are well known in the art. Suitable catalysts
wherein the functional groups are hydroxy, carboxy or include, but are not limited to, alkoxy titanium corn
amino. Advantageous difunctional sulfomonomer com pounds, alkali metal hydroxides and alcoholates, salts of
ponents are those wherein the sulfonate salt group is 5 organic carboxylic acids, alkyl tin compounds and
attached to an aromatic acid nucleus such as benzene, metal oxides.
naphthalene, diphenyl, oxydiphenyl, sulfonyldiphenyl The sulfopolyesters of this invention are useful as
or methylenediphenyl nucleus. Examples of sulfomo adhesives, coating materials, sizes, laminated products,
nomers include sulfophthalic acid, sulfoterephthalic aqueous printing inks, and films. Particular utility is
acid, sulfoisophthalic acid, 5-sodiosulfoisophthalic acid, found in applications where increased abrasion resis
4-sulfonaphthalene-2,7-dicarboxylic acid, and their es tance, inherent higher temperature process conditions,
ters. Metallosulfoaryl sulfonate which is described in and improved blocking resistance are required.
U.S. Pat. No. 3,779,993, and is incorporated herein by The materials and testing procedures used for the
reference, may also be used as a sulfomonomer. results shown herein are as follows:
The sulfomonomer is present in an amount to provide 15 CARBOWAX 600 is a trademark for a polyethylene
water-dispersibility to the sulfopolyester. It is possible
to adjust the water-dispersibility of the sulfopolyester glycol having a number average molecular weight (Mn)
by varying the mole percentage of sulfomonomer. Pref. of 600 daltons.
erably, the sulfomonomer is present in an amount of Glass transition temperature (Tg) was determined
from 5 to 40 mole percent, more preferably 8 to 30 mole using a differential scanning calorimeter (DSC).
percent, and most preferably 15 to 25 mole percent, Inherent viscosity (I.V.) was measured at 23° C. using
based on the sum of the moles of total dicarboxylic acid 0.50 grams of polymer per 100 ml of a solvent consisting
Cotent. of 60% by weight phenol and 40% by weight tetrachlo
Semi-crystalline and amorphous materials are within roethane.
the scope of the present invention. It is to be understood 25 The process of the present invention will be further
that the sulfopolyesters of this invention contain sub illustrated by a consideration of the following examples,
stantially equal molar proportions of acid equivalents which are intended to be exemplary of the invention.
(100 mole %) to hydroxy equivalents (100 mole %). All parts and percentages in the examples are on a
Thus, the sulfopolyester comprised of components (a), weight basis unless otherwise stated.
(b), (c), and (d) will have a total of acid and hydroxyl 30 EXAMPLE 1.
equivalents equal to 200 mole percent. The sulfopolyes
ters have an inherent viscosity of 0.1 to 1.0 dl/g, prefer Isophthalate-Based Sulfopolyester containing 19
ably 0.2 to 0.6dl/g. mole % 5-sodiosulfoisophthalate.
A buffer is preferably added to the compositions of A 500 mL flask was equipped with a head having a
the present invention. Buffers and their use are well 35 nitrogen inlet, a sidearm to allow removal of volatile
known in the art and do not require extensive discus materials, and a socket joint to accommodate a stirrer.
sions. Preferred buffers include sodium acetate, potas The stirrer shaft was inserted through the socket joint
sium acetate, lithium acetate, sodiumphosphate mono and has a ball joint attached by pressure tubing to the
basic, potassium phosphate dibasic and sodium carbon shaft, which provides a vacuum seal. The flask is
ate. The buffer is present in an amount of up to 0.2 moles charged with 29.1 grams (0.15 moles) dimethylisophtha
per mole of difunctional sulfomonomer. Preferably, the late, 61.0 grams (0.25 moles) dimethyl-2,6-naphthalene
buffer is present in an amount of about 0.1 moles per dicarboxylate, 29.6 grams (0.1 moles) dimethyl-5-sodi
mole of difunctional sulfomonomer. osulfoisophthalate, 66.2 grams (0.46 moles) 1,4-
The sulfopolyesters can be prepared by conventional cyclohexanedimethanol, 9.3 grams (0.15 moles) ethyl
polycondensation procedures well-known in the art. 45
ene glycol, 0.82 grams (0.01 moles) sodium acetate, and
Such processes include direct condensation of the dicar 0.45 mL of a 1.46% (w/w) solution of titanium(IV)
boxylic acids with the diol(s) or by ester interchange isopropoxide in n-butanol. After the reactants were
using lower alkyl esters. For example, a typical proce purged with nitrogen the flask was immersed in a Bel
dure consists of two stages. The first stage, known as mont metal bath preheated to 200° C. for two hours
ester-interchange or esterification, is conducted in an 50 with stirring under a gentle sweep of inert gas. The
inert atmosphere at a temperature of 175 C. to 240 C. temperature of the bath was raised to 215 C. and the
for 0.5 to 8 hours, preferably 1 to 4 hours. The diols, reaction allowed to continue for an additional two
depending on their particular reactivities and the spe hours to complete the transesterification stage. The bath
cific experimental conditions employed, are commonly
used in molar excesses of 1.05 to 2.5 per mole of total 55 temperature was increased from 215 C. to 280 C. and
dicarboxylic acid. the nitrogen purge was replaced with a vacuum of <
The second stage, referred to as polycondensation, is 0.5 mm Hg. The flask was heated for about 10 minutes
conducted under reduced pressure at a temperature of under the reduced pressure before the viscosity of the
230 C. to 350° C., preferably 265 C. to 325 C., and molten material exceeded the capacity of the stirrer to
more preferably 270° C. to 290 Q. for 0.1 to 6 hours, 60 provide adequate surface renewal. At this time the flask
preferably 0.25 to 2 hours. Because high melt viscosities was removed from the metal bath and the vacuum was
are encountered in the polycondensation stage, it is assuaged with a nitrogen sparge.
sometimes advantageous to employ temperatures above After the polymer had cooled to room temperature it
300 C. since the resulting decrease in melt viscosity was removed from the flask. Analysis of the polymer
allows somewhat higher molecular weights to be ob 65 indicated that the diol component consisted of approxi
tained. Stirring or appropriate conditions are employed mately 85 mole % 1,4-cyclohexanedimethanol and ap
in both stages to ensure sufficient heat transfer and proximately 15 mole % diethylene glycol. The test
surface renewal for the reaction mixture. The reactions results are summarized in Table I.
 5,369,210
7 8
EXAMPLE 2
mix of 95 mole % ethylene glycol and 5 mole % diethyl
ene glycol. The test results are summarized in Table I.
Terephthalate-Based Water-Dispersible Polyester EXAMPLE 7
Containing 20 Mole % 5-Sodiosulfoisophthalate
The apparatus and procedure used is described in 5 Relationship of Aliphatic Acid Modification to Tg.
Example 1. The amounts of reactants were initially The apparatus and procedure used is described in
charged to the flask: 29.1 grams (0.15 moles) dimethyl- Example 1. A polyester was prepared with 2 mole %
terephthalate, 61.0 grams (0.25 moles) dimethyl-2,6- succinic acid, 79 mole % dimethyl-2,6-naph
naphthalenedicarboxylate, 29.6 grams (0.1 moles) di- thalenedicarboxylate, 19 mole % 5-sodiosulfoisophtha
methyl-5-sodiosulfoisophthalate, 66.2 grams (0.46 10 late and a diol component of ethylene glycol. The test
moles) 1,4-cyclohexanedimethanol, 9.3 grams (0.15 results are summarized in Table I.
moles) ethylene glycol, 3.0 grams (0.005 moles) CAR
BOWAX 600, 0.52 grams (0.01 moles) sodium acetate, EXAMPLE 8
and 0.46 mL of a 1.46% (w/w) solution of titanium(IV) Relationship of Aliphatic Acid Modification to Tg.
isopropoxide in n-butanol. The transesterification stage 15 The apparatus and procedure used is described in
was conducted at 200 C. for two hours and 25 C. for Example 1. A polyester was prepared with 10 mole %
two hours with the continuous removal of methanol by succinic acid, 71 mole % dimethyl-2,6-naph
distillation. The second stage, also known as the poly- thalenedicarboxylate, 19 mole % 5-sodiosulfoisophtha
merization stage, was performed at a reduced pressure late and a diol component of ethylene glycol. The test
between 0.05 to 0.5 mm Hg at a temperature of 280 C. 20 results are summarized in Table I.
for ten minutes. Examples 5 to 8 illustrate how the molar amount of
Analysis of the polymer indicated that the diol com- incorporation and chain length of an aliphatic acid low
ponent consisted of approximately 88 mole % 1,4- ers the Tg of a polymer based on naphthalene units.
cyclohexanedimethanol, approximately 11 mole % di
ethylene glycol, and 1 mole % CARBOWAX 600. The 25 EXAMPLES 9-10
test results are summarized in Table I. Effect of PEG Incorporation on IV and Tg
The apparatus and procedure used is described in
EXAMPLE 3 Example 1. Two polyesters containing approximately
(Comparative) No Naphthalene Modification 21 mole % 5-sodiosulfoisophthalate and approximately
The apparatus and procedure used is described in 30 80 mole % 1,4-cyclohexanedimethanol are modified
Example 1. A polyester was prepared with 81 mole % with 0.3 and 1.7 mole % of a polyethylene glycol hav
isophthalic acid, 19 mole % 5-sodiosulfoisophthalate ing a molecular weight of 1000 daltons, respectively.
and a diol mix of 86 mole % 1,4-cyclohexanedime- The inherent viscosity increased from 0.28 to 0.31 with
thanol, 12 mole % ethylene glycol, and 2 mole % dieth- a concomitant decrease in Tg from 110 to 105 C. The
ylene glycol. The test results are summarized in Table I. 35 test results are summarized in Table I.
EXAMPLE 4 EXAMPLES 11-12
Efficacy of Naphthalene Modification Effect of SIP Level on Tg
The apparatus and procedure used is described in The apparatus and procedure used is described in
Example 1. A polyester was prepared with 29 mole % 40 Example 1. Two polyesters differing only in amount of
isophthalic acid, 52 mole % dimethyl-2,6-naph- SIP level are determined to have Tg's of 98 and 100° C.
thalenedicarboxylate, 19 mole % 5-sodiosulfoisophtha- for SIP levels of 15 and 20 mole %, respectively. The
late and a diol mix of 87 mole % 1,4-cyclohexanedime- amounts and test results are summarized in Table I.
thanol, 10 mole % ethylene glycol, and 3 mole % dieth
ylene glycol. The test results are summarized in Table I. 45 EXAMPLES 13-14
Importance of Diol Component Identity to Tg
EXAMPLE 5 The apparatus and procedure used is described in
Relationship of Aliphatic Acid Modification to Tg. Example 1. Two polyesters containing different diol
The apparatus and procedure used is described in ratios of DEG/EG are compared which shows the
Example 1. A polyester was prepared with 5 mole % 50 critical nature of the diol component to Tg. The ratios
sebacic acid, 77 mole % dimethyl-2,6-naphthalenedicar- and test results are summarized in Table I.
boxylate, 18 mole % 5-sodiosulfoisophthalate and a diol
mix of 94 mole % ethylene glycol and 6 mole % diethyl- EXAMPLES 15-17
ene glycol. The test results are summarized in Table I. Relationship of Aliphatic Glycol Modification to Tg
55 The apparatus and procedure used is described in
EXAMPLE 6 Example 1. Examples 15-17 illustrate that both the
Relationship of Aliphatic Acid Modification to Tg. molar amount of incorporation and chain length of an
The apparatus and procedure used is described in aliphatic glycol affects the Tg of a particular composi
Example 1. A polyester was prepared with 13 mole % tion. The amount, chain length of the glycols and test
sebacic acid, 69 mole % dimethyl-2,6-naphthalenedicar- 60 results are summarized in Table I.
boxylate, 18 mole % 5-sodiosulfoisophthalate and a diol
TABLE I
Dicarboxylic Water
Acid Diol SIP Dispersibility Tg
Example (Mole %) (Mole %) (Mole %) IV at 80° C. (wt %) (C)
N (51) CHDM (85) 19 0.30 15 109
I (30) EG (15)
2 N (46) CHDM (88) 22 0.3 15 117
 5,369,210
9 10
TABLE I-continued
Dicarboxylic Water
Acid Diol SP Dispersibility Tg
Example (Mole %) (Mole %) (Mole %) IV at 80 C. (wt %) ("C.)
T (32) EG (11)
PEG600
3 I (81) CHDM (86) 19 0.23 30 87
(Control) EG (12)
DEG (2)
4. N (52) CHDM (87) 19 0.23 2O 97
I (29) EG (10)
DEG (3)
5 N (77) EG (94) 18 0.18 30 114
SB (5) DEG (6)
6 N (69) EG (95) 18 0.20 30 86
SB (13) DEG (5)
7 N (79) EG (100) 19 0.20 30 119
SC (2)
8 N (71) EG (100) 19 0.20 30 109
SC (10)
9 N (52) CHDM (77) 21 0.28 5 10
I (27) EG (23)
PEG1000 (3)
10 N (52) CHDM (80) 20 0.31 5 105
I (28) EG (18)
PEG1000 (2)
11 T (73) EG (96) 15 0.22 30 98
N (12) DEG (4)
12 T (69) EG (95) 20 0.18 30 100
N (11) DEG (5)
13 I (37) EG (95) 21 0.21 30 90
N (22) DEG (5)
14 I (38) EG (40) 20 0.24 30 60
N (22) DEG (60)
15 N (53) EG (74) 20 0.14 30 90
T (27) BD (26)
16 N (50) EG (66) 21 0.3 3O 79
T (29). BD (34)
17 N (50) EG (60) 20 0.21 30 71
T (30) HD (40)
KEY TO ABBREVIATIONS
BD = i,4-butanediol
CHDM = 1,4-cyclohexanedimethanol
DEG = diethylene glycol
EG = ethylene glycol
HD = 1,6-hexanediol
I = isophthalic acid or dimethyl isophthalate
N = dimethyl-2,6-naphthalene dicarboxylate
PEG600 = poly(ethylene glycol)
PEG1000 = polyethylene glycol
SB = sebacic acid
SC = succinic acid
SIP = 5-sodiosulfoisophthalate
T = terephthalic acid or dimethyl terephthalate

In Examples 18-27, a parallel plate mechanical spec

trometer was used to determine the melt viscosities at
275 C. over a range of frequencies. An Instron capil data for the polyesters used in the melt viscosity deter
lary rheometer was used to obtain melt viscosity data SO minations are provided in Table II.
for Examples 27 and 28 at 275 C. over a range of shear EXAMPLES 22 and 23
lates.
EXAMPLES 18 and 19 Examples 22 and 23 indicate that even small amounts
of incorporated aliphatic acids yield a composition with
Examples 18 and 19 indicate that incorporation of 55 a high Tg and reduced melt viscosity. The composi
napthalenediyl units raises the Tg of an all isophthalate tional and characterization data for the polyesters used
composition, but results in a lower melt viscosity even in the melt viscosity determinations are provided in
though the level of SIP is higher for the modified sys Table II.
tem. The compositional and characterization data for EXAMPLES 24 and 25
the polyesters used in the melt viscosity determinations
are provided in Table II. Examples 24 and 25 indicate that the modified sys
EXAMPLES 20 and 21 tems have lower melt viscosities at much higher molec
ular weights. In addition, the all-naphthalene composi
Examples 20 and 21 indicate that a isophthalate/- tion contains predominately EG while the modified
naphthalate system may have a significantly higher 65 composition is mainly CHDM; normally CHDM results
molecular weight and lower melt viscosity than an in a higher melt viscosity than EG. The compositional
all-naphthalate composition without significantly low and characterization data for the polyesters used in the
ering the Tg. The compositional and characterization melt viscosity determinations are provided in Table II.
 5,369,210
11 12
EXAMPLES 26 and 27 -continued
Examples 26 and 27 are comparative examples which TORQUE DATA (Temperature as 275 +/- 1. C.)
indicate that increasing the cycloaliphatic diol (i.e., 901.7 6
8892 10
CHDM) content, while decreasing the glycol ether (i.e., 5 8705 16
DEG) content, results in a higher melt viscosity. The 8474 25
compositional and characterization data for the polyes 8175 40
ters used in the melt viscosity determinations are pro 7790 63
7293 100
vided in Table II. 6702 159
TABLE II O 6057 251
S410 398
Dicarboxylic EXAMPLE 2 (Control);
Acid Dio SIP Tg 30094 1.0
Example (Mole %) (Mole %) (Mole %) IV (°C) 26400 1.6
8 I (81) CHDM (86) 19 0.23 86 is 23020 2.5
EG (12) 20390 4
DEG (2) 18240 6
19 I (64) CHDM (85) 22 0.23 93 6460 10
N (14) EG (2) 4960 16
DEG (3) 3660 25
20 N (51) CHDM (76) 20 0.33 105 2500 40
I (29) DEG (24) 20 11420 63
2. N (80) CHDM (76) 20 0.26 110 030 100
DEG (24) 92.38 59
22 N (79) EG (98) 19 0.20 119 8205 2S1
SC (2) DEG (2) 7286 398
23 N (82) EG (93) 18 0.21 115 EXAMPLE 22: -
DEG (6) 25 4.170 O
PEG 1000 (1) 4.057 1.6
24 T (60) CHDM (81) 15 0.34 12 399 2.5
N (25) EG (17) 3752 4.
DEG (2) 3608 6
25 N (85) EG (72) 15 0.29 129 3474 10
CHDM (2) 3O 3349 16
DEG (7) 3233 25
26 I (81) CHDM (83) 19 0.32 84 324 40
DEG (17) 3.018 63
27 I (82) DEG (54) 8 0.34 54 2903 100
CHDM (46) 2768 159
35 2611 25
2430 398
EXAMPLE 23 (Control):
TORQUE DATA (Temperature = 275 +/- 1. C.) 7730 1.0
7706 1.6
Viscosity (Poise) Frequency (rad/s) 7668 2.5
EXAMPLE 18 (Control): 40 7612 4.
7081 1.0 7532 6
7024 1.6 7437 O
6970 2.5 7298 16
6908 4. 71.4 25
6846 6 6872 40
6755 O 45 6550 63
6635 6 640 100
6480 25 5654 159
6278 40 5118 251
604 63 4575 398
5665 100 EXAMPLE 24: -
5247 159 50 40670 1.0
477 25 39.650 1.6
428 398 38390 2.5
EXAMPLE 19: 36900 4
5534 1.0 3S220 6
5511 1.6 33260 10
5455 2.5 55 30950 16
5436 4. 2830 25
54.06 6 25370 40
5372 10 22280 63
5323 16 1950 100
52.54 25 1650 59
5162 40 60 13440 251
5028 63 TO 398
4834 100 EXAMPLE 25 (Control):
4573 159 5742O 10
42.54 251 56340 1.6
3908 398 S4850 2.5
EXAMPLE 2.0: 65 52860 4.
9300 1.0 50260 6
9236 1.6 46920 10
940 2.5 42920 6
909 4 38.430 25
 5,369,210
13 14
-continued (b) 2 to 85 mole percent of a dicarboxylic acid se
TORQUE DATA (Temperature = 275 +/- 1. C.)
lected from the group consisting of isophthalic
acid, terephthalic acid, dimethyl terephthalate, and
33700 40 dimethyl isophthalate. and combinations thereof;
28910 63 5
24270 100 (c) a diol wherein 0.1 to 5 mole percent of the diol is
20010 159 a polymeric diol having the formula HO-(OCH
16320 251 2-CH2)-OH, wherein x is 10 to 50; and
13350 398 (d) a difunctional sulfomonomer containing at least
Viscosity (poise) Shear Rate (1/s) one sulfonate group attached to an aromatic nu
EXAMPLE 26: O cleus wherein the functional groups are hydroxy,
6500 4.5 carboxy or amino, provided the difunctional sul
6200 15 fomonomer is present in an amount from 15 to 25
6150
4800
45
150
mole percent based on 100 mole percent dicarbox
4200 450 15
ylic acid and 100 mole percent diol.
2700 1500 2. The sulfopolyester of claim 1 wherein the sul
.EXAMPLE 27: fopolyester is prepared using a buffer in an amount of
2100 4.5 0.001 to 0.2 moles per mole of difunctional sulfomo
2200 15 Ot.
2150 45 3. The sulfopolyester of claim 2 wherein the buffer is
1700 150
1500 450 20 present in an amount of 0.1 moles per mole of difunc
1200 1500 tional sulfomonomer.
4. The sulfopolyester of claim 2 wherein the buffer is
The results from Examples 18 to 28 indicate that the potassiumfrom
selected the group consisting of sodium acetate,
acetate, lithium acetate, sodium phosphate
melt viscosity of high Tg water-dispersible polyesters 25 monobasic, potassium phosphate dibasic and sodium
based on naphthalenediyl modification have lower melt carbonate.
viscosities than compositions having only napthalened 5. The sulfopolyester of claim 4 wherein the buffer is
iyl units. The compositions modified with naphtha Sodium acetate.
lenediyl units also have lower melt viscosities than the
higher Tg water-dispersible polyesters comprised of 30 componentsulfopolyester
6. The of claim 1 wherein the diol
is a mixture of ethylene glycol and diethyl
isophthaloyl units. Thus, compositions containing iso ene glycol.
phthalate and naphthalenediylic units retain a high Tg, 7. The sulfopolyester of claim 1 wherein the diol
however, particular compositions having a given Tg component is a mixture of diethylene glycol and 1,4-
will have lower melt viscosities than compositions pos cyclohexanedimethanol.
sessing only naphthalenediyl units at the same given Tg. 35 8. The sulfopolyester of claim 1 wherein the diol
In addition, compositions based on only isophthaloyl component is a mixture of ethylene glycol and polyeth
units having Tg values in the 80 C. to 89 C. range also ylene glycol.
have higher melt viscosities than the compositions con 9. The sulfopolyester of claim 8 wherein the polyeth
taining both isophthalate and naphthalenediyl units. ylene glycol is present in an amount of 1 to 4 mole
Many variations will suggest themselves to those skilled 40 percent.
in this art in light of the above detailed description. All 10. The sulfopolyester of claim 1 wherein the diol
such obvious modifications are within the full intended component is a mixture of diethylene glycol and poly
scope of the appended claims. ethylene glycol.
What is claimed is: 11. The sulfopolyester of claim 1 wherein the difunc
1. A water-dispersible sulfopolyester having a glass 45 tional sulfomonomer component is selected from the
transition temperature of greater than 89 C. and low group consisting of sulfophthalic acid, sulfoterephthalic
melt viscosity consisting essentially of repeat units from: acid, sulfoisophthalic acid, 4-sulfonaphthalene-2,7-
(a) 10 to 93 mole percent of a dicarboxylic acid se dicarboxylic acid, and esters thereof.
lected from the group consisting of naphthalene 12. The sulfopolyester of claim 10 wherein the di
2,6-dicarboxylic acid, naphthalene-2,7-dicarboxy- 50 functional sulfomonomer component is 5-sodiosul
lic acid, naphthalene-2,6-dicarboxylate ester and foisophthalic acid.
naphthalene-2,7-dicarboxylate ester; ck k k k k

55

60

65