U.S. patent number RE39,617 [Application Number 10/655,988] was granted by the patent office on 2007-05-08 for butadiene polymers having terminal functional groups.
This patent grant is currently assigned to Kraton Polymers US LLC. Invention is credited to Daniel E. Goodwin, Dale L. Handlin, Jr., Michael J. Modic, David J. St. Clair, Craig A. Stevens, John D. Wilkey, Carl L. Willis.
United States Patent |
RE39,617 |
Handlin, Jr. , et
al. |
May 8, 2007 |
Butadiene polymers having terminal functional groups
Abstract
Hydrogenated butadiene polymers having terminal functional
groups have minimum viscosity at any molecular weight when the
1,2-addition is between 30% and 70% Hydrogenated butadiene polymers
having about two terminal hydroxyl groups per molecule have
surprisingly lower viscosities at 30% to 70% 1,2-addition than
similar polymers having either higher or lower amounts of
1,2-addition. The polymers are useful in making coatings, sealants,
binders, and block copolymers with polyesters, polyamides, and
polycarbonates.
Inventors: |
Handlin, Jr.; Dale L. (Houston,
TX), Goodwin; Daniel E. (Katy, TX), Willis; Carl L.
(Houston, TX), St. Clair; David J. (Houston, TX), Wilkey;
John D. (Owasso, OK), Modic; Michael J. (Houston,
TX), Stevens; Craig A. (Marietta, OH) |
Assignee: |
Kraton Polymers US LLC (Belpre,
OH)
|
Family
ID: |
25472204 |
Appl.
No.: |
10/655,988 |
Filed: |
September 5, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
07938917 |
Aug 31, 1992 |
5393843 |
|
|
Reissue of: |
08306552 |
Sep 15, 1994 |
05405911 |
Apr 11, 1995 |
|
|
Current U.S.
Class: |
525/139; 525/170;
525/171; 525/182; 525/183; 525/184; 525/332.8; 525/332.9;
525/333.1; 525/333.2; 525/378; 525/379; 525/383; 525/384;
525/386 |
Current CPC
Class: |
C08C
19/44 (20130101); C08F 136/06 (20130101); C08G
18/0823 (20130101); C08G 18/6208 (20130101); C08G
18/8175 (20130101); C08G 63/00 (20130101); C08G
64/18 (20130101); C08G 69/00 (20130101); C08G
81/024 (20130101); C08L 15/00 (20130101); C08L
19/006 (20130101); C08F 136/06 (20130101); C08F
4/488 (20130101); C08G 18/8175 (20130101); C08G
18/62 (20130101) |
Current International
Class: |
C08F
8/00 (20060101) |
Field of
Search: |
;525/139,170,171,182,183,184,332.8,332.9,333.1,333.2,378,379,383,384,386 |
References Cited
[Referenced By]
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WO |
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Other References
Yves Camberlin et al.; Synthesis and Properties of Partially or
Fully Hydrogenated Dienic Oligomers, Macromol. Chem 180 2309-2321
(1979), 3 Tables, 9 Figs. cited by other .
A. J. Di Milo et al.; Saturated Hydrocarbon Polymers for Solid
Rocket Propellants, J. Macromol. Sci-Chem, A3(7), Nov. 1969, pp.
1419-1442, 8 Tables, 15 Figs. cited by other .
Karel Bouchal et al.; The Hydrogenation of HO-Terminated Telechelic
Polybutadienes in the Presence of a Homogeneous Hydrogenation
Catalyst Based on Tris(triphenylphosphine) rhodium Chloride,
Angewandre Makromoleculare Chemic 165 (1989) pp. 165-180 (Nr.
2716). cited by other .
P. Lutz, E. Franta & P. Rempp, "An Efficient Bifunctional
Lithium-Organic Initiator To Be Used in Apolar Solvents", 1982, pp.
1953-1959. cited by examiner .
F. Bandermann, H. Speikamp & L. Weigel, "Bifunctional Anioic
Initiators", Makromol. Chem., 2017-2024 (1985). cited by examiner
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G. Bienert et al., "A Bifunctional Anioic Initiator Soluble in
Polar Solvents", Makromol. Chem. 179, 551-555 (1978). cited by
examiner .
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by examiner.
|
Primary Examiner: Lipman; Bernard
Attorney, Agent or Firm: Tyler; Gene L.
Parent Case Text
This is a division of application Ser. No. 07/938,917, filed Aug.
31, 1992.
Claims
We claim:
1. A polymer composition, produced by the steps of: reacting one or
more compounds with the terminal functional groups on a polymer,
and said polymer consists essentially of: polymerized 1,3-butadiene
having a peak molecular weight between 500 and 20,000, 1,2-addition
between 30% and 70%, and hydrogenation of at least 90% of the
unsaturation; .Iadd.a ratio of viscosity (in poise at room
temperature) to peak molecular weight raised to the 3.4 power of at
most 2.0 times 10.sup.-9; .Iaddend.and .[.one.]. .Iadd.about two
.Iaddend.or more terminal functional groups per molecule.
2. The polymer .Iadd.composition .Iaddend.of claim .[.1.].
.Iadd.6.Iaddend., wherein the terminal functional groups .Iadd.of
the polymer .Iaddend.are selected from .[.a.]. .Iadd.the
.Iaddend.group consisting of hydroxyl, carboxyl, phenol, epoxy, and
amine groups.
.[.3. The polymer of claim 2, wherein the polymer has a ratio of
viscosity (poise at room temperature) to peak molecular weight
raised to the 3.4 power of at most 2.0.times.10.sup.-9..].
4. The polymer .Iadd.composition .Iaddend.of claim .[.3.].
.Iadd.6.Iaddend., wherein the polymerized
.Iadd.1,3-.Iaddend.butadiene has a peak molecular weight between
1,000 and 10,000.
5. The polymer .Iadd.composition .Iaddend.of claim 4, wherein the
polymerized .Iadd.1,3-.Iaddend.butadiene is at least 95%
hydrogenated.
6. The polymer .Iadd.composition .Iaddend.of claim .[.5.].
.Iadd.1.Iaddend., wherein the ratio of viscosity to peak molecular
weight raised to the 3.4 power .Iadd.of the polymer .Iaddend.is
less than 1.0 .[..times..]. .Iadd.times .Iaddend.10.sup.-9.
7. The polymer .Iadd.composition .Iaddend.of claim 6, wherein the
terminal functional groups .Iadd.of the polymer .Iaddend.consist of
about two hydroxyl groups per molecule.
8. The polymer .Iadd.composition .Iaddend.of claim 1, wherein the
peak molecular weight .Iadd.of the polymer .Iaddend.is between 1000
and 10000.
9. The polymer .Iadd.composition .Iaddend.of claim .[.8.].
.Iadd.6.Iaddend., wherein the 1,2-addition of the polymerized
.Iadd.1,3-.Iaddend.butadiene is between 40% and 60%.
10. The polymer composition of claim 1, wherein the polymerized
1,3-butadiene has about two hydroxyl groups per molecule.
11. The .[.polymeric.]. .Iadd.polymer .Iaddend.composition of claim
10, wherein the polymerized 1,3-butadiene is reacted with compounds
that form a coating.
12. The .[.polymeric.]. .Iadd.polymer .Iaddend.composition of claim
10, wherein the polymerized 1,3-butadiene is reacted with compounds
that form a block selected from .Iadd.the group consisting of
.Iaddend.polyesters, polyamides, and polycarbonates.
.Iadd.13. The polymer composition of claim 8 wherein the polymer
has a peak molecular weight of about 10,000..Iaddend.
.Iadd.14. The polymer composition of claim 8 wherein the polymer
has a peak molecular weight of about 5,000..Iaddend.
.Iadd.15. The polymer composition of claim 8 wherein the polymer
has a peak molecular weight of about 3,000..Iaddend.
.Iadd.16. The polymer composition of claim 8 wherein the polymer
has a peak molecular weight of about 2,000..Iaddend.
.Iadd.17. The polymer composition of claim 4 wherein the polymer
has a peak molecular weight of about 10,000..Iaddend.
.Iadd.18. The polymer composition of claim 4 wherein the polymer
has a peak molecular weight of about 5,000..Iaddend.
.Iadd.19. The polymer composition of claim 4 wherein the polymer
has a peak molecular weight of about 3,000..Iaddend.
.Iadd.20. The polymer composition of claim 4 wherein the polymer
has a peak molecular weight of about 2,000..Iaddend.
.Iadd.21. The polymer composition of claim 1 wherein the
polymerized 1,3-butadiene has 1.7 terminal functional groups per
molecule..Iaddend.
.Iadd.22. The polymer composition of claim 1 wherein the
polymerized 1,3-butadiene has 1.9 terminal functional groups per
molecule..Iaddend.
Description
BACKGROUND OF THE INVENTION
This invention relates to manufacture of low viscosity hydrogenated
butadiene polymers having terminal functional groups and use of the
low viscosity polymers to make coatings and other high molecular
weight polymers.
Anionic polymerization of conjugated dienes with lithium
initiators, such as sec-butyllithium, and hydrogenation of residual
unsaturation has been described in many references including U.S.
Pat. No. Re. 27,145 which teaches a relationship between the amount
of 1,2-addition of butadiene (35% to 55%) and the glass transition
temperatures of the hydrogenated butadiene polymers.
The termination of living anionic polymers to form functional end
groups is described in U.S. Pat. Nos. 4,417,029, 4,518,753, and
4,753,991. Of particular interest for the present invention are
terminal hydroxyl, carboxyl, phenol, epoxy, and amine groups.
For unsaturated 1,3-butadiene polymers it is known that low
1,2-addition is necessary to obtain low viscosity as taught in U.S.
Pat. Nos. 4,518,753 and 3,652,732. However, when these polymers are
hydrogenated they are crystalline solids. Such a crystalline
polymer is available from Mitsubishi and is designated POLYTAIL H
polymer which has a melting point of 72.degree. C.
The hydrogenated butadiene polymers are non-crystalline when the
1,2-addition of butadiene is above 30% as described in U.S. Pat.
No. 4,020,125. The non-crystalline hydrogenated butadiene polymers
are viscous liquids at low molecular weights as described in U.S.
Pat. Nos. 4,866,120 and 4,020,125. POLYTAIL HA polymer produced by
Mitsubishi and NISSO GI-2000 polymer produced by Nippon Soda are
commercial examples of low molecular weight hydrogenated butadiene
polymers which have terminal functional groups and 1,2-addition of
about of 84%.
It is an object of the present invention to provide hydrogenated
butadiene polymers having terminal functional groups and low
viscosity at room temperature. It is also an object of the
invention to use the low viscosity polymers to make coatings and
other high molecular weight polymers.
SUMMARY OF THE INVENTION
Applicants have discovered that varying the amount of 1,2-addition
of butadiene in hydrogenated butadiene polymers having terminal
functional groups significantly and unexpectedly impacts the
viscosity of the polymers. The lowest viscosity for any given
molecular weight of a hydrogenated butadiene polymer having
terminal functional groups is achieved when the 1,2-addition is
between 30% and 70%, preferably between 40% and 60%.
The hydrogenated butadiene polymers of the invention may be used
without solvents at room temperature when the peak molecular
weight, as measured by gel permeation chromatography, is between
500 and 20,000, preferably between 1,000 and 10,000.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plot of the relationship between vinyl content and
viscosity of hydrogenated 1,3-butadiene polymers having terminal
functional groups. The viscosity data are adjusted to remove
molecular weight contributions by dividing the viscosity by the
peak molecular weight raised to the 3.4 power.
DETAILED DESCRIPTION OF THE INVENTION
Anionic polymerization of conjugated diene hydrocarbons with
lithium initiators is well known as described in U.S. Pat. Nos.
4,039,593 and Re. 27,145 which descriptions are incorporated herein
by reference. Polymerization commences with a monolithium,
dilithium, or polylithium initiator which builds a living polymer
backbone at each lithium site. Typical living polymer structures
containing polymerized conjugated diene hydrocarbons are: X--B--Li
X--A--B--Li X--A--B--A--Li Li--B--Y--B--Li Li--A--B--Y--B--A--Li
wherein B represents polymerized units of one or more conjugated
diene hydrocarbons such as butadiene or isoprene, A represents
polymerized units of one or more vinyl aromatic compounds such as
styrene, X is the residue of a monolithium initiator such as
sec-butyllithium, and Y is the residue of a dilithium initiator
such as the diadduct of sec-butyllithium and
m-diisopropenylbenzene. Some structures, including those pertaining
to polylithium initiators or random units of styrene and a
conjugated diene, generally have limited practical utility although
known in the art.
The anionic polymerization of the conjugated diene hydrocarbons is
typically controlled with structure modifiers such as diethylether
or glyme (1,2-diethoxyethane) to obtain the desired amount of
1,4-addition. As described in Re 27,145 which is incorporated by
reference herein, the level of 1,2-addition of a butadiene polymer
or copolymer can greatly affect elastomeric properties after
hydrogenation.
The 1,2-addition of 1,3-butadiene polymers having terminal
functional groups significantly and surprisingly influences the
viscosity of the polymers as described in more detail below. A
1,2-addition of about 40% is achieved during polymerization at
50.degree. C. with about 6% by volume of diethylether or about 1000
ppm of glyme.
Dilithium initiation with the diadduct of sec-butyllithium
(s--BuLi) and m-diisopropenylbenzene also requires presence of a
non-reactive coordinating agent such as diethyl ether, glyme, or
triethyl amine, otherwise monolithium initiation is achieved. Ether
is typically present during anionic polymerization as discussed
above, and the amount of ether typically needed to obtain specific
polymer structures has been sufficient to provide dilithium
initiation.
Anionic polymerization is often terminated by addition of water to
remove the lithium as lithium hydroxide (LiOH) or by addition of an
alcohol (ROH) to remove the lithium as a lithium alkoxide (LiOR).
For polymers having terminal functional groups, the living polymer
chains are preferably terminated with hydroxyl, carboxyl, phenol,
epoxy, or amine groups by reaction with ethylene oxide, carbon
dioxide, a protected hydroxystyrene monomer, ethylene oxide plus
epichlorohydrin, or the amine compounds listed in U.S. Pat. No.
4,791,174, respectively.
Termination with ethylene oxide results in release of fine
particles of lithium bases as described in U.S. Pat. application
Ser. No. 07/785,715, now U.S. Pat. No. 5,166,277 which is
incorporated by reference herein. The lithium bases interfere with
hydrogenation of the polymer and preferably are removed.
Termination with carbon dioxide results in carboxylate salt groups
that reduce hydrogenation catalyst activity as described in U.S.
Pat. No. 4,970,254, which disclosure is incorporated by reference
herein. Improved hydrogenation is obtained by converting the
carboxylate salt groups to ester groups prior to hydrogenation and
then reconverting to carboxylate salt or carboxylic acid groups
after hydrogenation.
Hydrogenation of at least 90%, preferably at least 95% of the
unsaturation in low molecular weight butadiene polymers is achieved
with nickel catalysts as described in U.S. Pat. No. Re. 27,145 and
4,970,254 and U.S. Pat. application Ser. No. 07/785,715 which are
incorporated by reference herein. The preferred nickel catalyst is
a mixture of nickel 2-ethylhexanoate and triethylaluminum described
in more detail in Example 1 below.
Butadiene polymers having two or more terminal functional groups
selected from hydroxyl, carboxyl, phenol, epoxy, and amine groups
can be used without solvents when the viscosity of the polymer is
less than about 500 poise. These functional groups do not exhibit
significant atomic attractions that would otherwise solidify the
functionalized polymers. Hydrogenated butadiene polymers having a
lower viscosity than 500 poise are produced by limiting the peak
molecular weight to a range from 500 to 20,000 and by limiting the
1,2-addition to an amount between 30% and 70%, preferably between
40% to 60%.
It is well known that the viscosity of higher molecular weight
polymers is proportional to molecular weight raised to the 3.4
power as described by D. W. Van Krevelen, "Properties of Polymers"
Elsevier Scientific Pub Co., New York, 1976, pp. 337-339, and J. D.
Ferry, "Viscoelastic Properties of Polymers" John Wiley & Sons,
New York, 1970, pp 267-271. For low molecular weight polymers
having no functional groups, viscosity is proportional to molecular
weight to the first power. Low molecular weight polymers having
terminal functional groups behave like higher molecular weight
polymers. Therefore, in comparing the viscosity of low molecular
weight polymers having terminal functional groups, viscosity data
must be adjusted for molecular weight variations by dividing
measured viscosity by molecular weight raised to the 3.4 power.
The polymers of the invention have the conventional utilities such
as forming coatings, sealants, and binders. In addition, the
butadiene polymers having about two or more terminal hydroxyl
groups can be co-polymerized with conventional compounds during
production of polycarbonates, polyesters, and polyamides as
described in U.S. Pat. No. 4,994,526 which is incorporated herein
by reference.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Hydrogenated 1,3-butadiene polymers having about two terminal
groups per molecule and unexpectedly low viscosity have been
produced by controlling the 1,2-addition of the butadiene. Such
polymers are low viscosity liquids at room temperature when the
peak molecular weight of the polymer ranges between 1,000 and
10,000, as measured by gel permeation chromatography using
polybutadiene standards, and the 1,2-addition ranges from 40% to
60%. The examples below show that 1,2-addition of the hydrogenated
butadiene polymers has an unexpected effect on viscosity.
The peak molecular weights were measured using gel permeation
chromatography calibrated with polybutadiene standards having known
peak molecular weights. The solvent for all samples was
tetrahydrofuran.
The 1,2-additions vinyl contents was measured by C.sup.13 NMR in
chloroform solution.
The viscosities were measured at room temperature on a Rheometrics
Dynamic Mechanical Spectrometer in dynamic oscillatory mode at a
frequency of 10 radians per second. Viscosity measurements were
adjusted for comparison by division with peak molecular weight
raised to the 3.4 power. Peak molecular weights are believed to
best indicate molecular weight variations in the polymers of this
invention and are determined from standards having known peak
molecular weights rather than by approximation.
EXAMPLE 1
A linear hydrogenated butadiene polymer having about two terminal
hydroxyl groups per molecule, a peak molecular weight of 2900, as
determined by Gel Permeation Chromatography (GPC) using
polybutadiene standards, and a 1,2-addition of 40%, as determined
by a Nuclear Magnetic Resonance (NMR) technique, was prepared as
described below. The linear butadiene precursor polymer was
synthesized using a diinitiator for the polymerization of
1,3-butadiene. The living polymer chain ends were capped using
ethylene oxide to afford the precursor polymer having terminal,
primary hydroxyl functionality. This polymer was hydrogenated using
a Ni/Al catalyst.
To synthesize the diinitiator moiety, 100 pounds of cyclohexane, 6
pounds of diethyl ether, and 1564 g of m-diisopropenylbenzene
(DIPB) (97% wt DIPB, 9.6 moles) were combined with stirring in a
sealed, steel reactor vessel under an inert, nitrogen atmosphere.
Impurities that might interfere with anionic polymerization were
removed by titration with a solution of s--BuLi in cyclohexane
(0.09 g of s--BuLi/ml). The purified solution was then treated with
2 equivalents of s--BuLi (23.5 pounds of s--BuLi solution, 19
moles) for each equivalent of DIPB that was present. Reaction at
50.degree. C. for 30 minutes gave a solution of the expected
diinitiator. The structure of the diinitiator was verified by
analyzing a methanol quenched aliquot of the solution using a gas
chromatography-mass spectroscopy (GC-MS) technique.
In a separate vessel, 162 pounds of cyclohexane, 15 pounds of
diethyl ether, and 42 pounds of polymerization grade 1,3-butadiene
were combined under a nitrogen atmosphere at 20.degree. C. As
described above, the solution was titrated with. s--BuLi reagent to
remove impurities that would interfere with the anionic
polymerization of butadiene. The purified solution of monomer was
transferred to the vessel containing the diinitiator and
polymerization ensued. The polymerization exotherm was controlled
by cooling the reactor to keep the temperature of the reaction
mixture below 50.degree. C. After 30 minutes, the polymerization
reaction was essentially complete. An alpha, omega-polymer lithium
species (Li--B--Y--B--Li) had been synthesized.
The solution containing the diinitiated polymer was treated, at
50.degree. C., with 7.5 pounds of ethylene oxide (77 moles) to
insert --C--C--O-- at the polymer chain ends to form alkoxide
polymer chain ends, --C--C--C--O--Li. Reaction was allowed to
proceed for 3 hours. At this point, the reaction mixture was a
solid rubbery mass resulting from the formation of an ionic gel
derived from association of the alkoxide polymer chain ends.
Treatment of the gel with 610 g of methanol afforded a free flowing
solution of a polybutadiene diol having --C--C--O--H end caps and a
precipitate of lithium methoxide (LiOMe). The precipitate was
allowed to settle in the reactor overnight.
A LiOMe slurry was drained from the bottom of the vessel and
discarded. An aliquot of the clear solution of the butadiene
polymer having terminal hydroxyl groups was analyzed via GPC and
found to contain a single polymeric species having a peak molecular
weight of 2900. Average molecular weights were calculated from the
GPC data as M(n)=2470 and M(w)=2940.
Analysis by C(13)NMR found the 1,2-addition to be 40% and the
ethylene oxide end capping efficiency was 82% (100 times the ratio
of moles of --C--C--O--H end caps to moles of s--BuLi
initiator).
A 10 gallon aliquot of the solution of the butadiene polymer having
terminal hydroxyl groups was transferred to a high pressure reactor
for hydrogenation using a Nickel/Aluminum catalyst. The catalyst
was prepared in advance by reacting nickel 2-ethylhexanoate with
triethylaluminum in cyclohexane in amounts sufficient to give a
ratio of 2.6 moles of aluminum to 1 mole of nickel. The polymer
solution was sparged with hydrogen at 65.degree. C. The reactor was
then filled with hydrogen to a pressure of 810 psig. An initial
aliquot of the Ni/Al catalyst solution was then pressured into the
reactor in such a volume as to afford a Ni concentration of 100 ppm
in the reaction mixture. An exothermic hydrogenation reaction
ensued.
When the temperature of the reaction solution had stabilized, an
aliquot of the solution was analyzed by ozonolysis to check the
degree of hydrogenation of the polybutadiene diol. As hydrogenation
was incomplete, another aliquot of catalyst was added which lead to
an additional exotherm. This process was repeated until the
ozonolysis test showed essentially complete hydrogenation of the
polybutadiene diol (final reaction conditions - [Ni]=1900 ppm,
95.degree. C., 6 hr). An aliquot of the polymer solution was
analyzed by C(13)NMR, by this method of analysis, 95% of the
carbon-carbon unsaturation (--C.dbd.C--) had been hydrogenated and
there was no evidence of hydrogenolysis of the terminal hydroxyl
groups.
The hydrogenation catalyst was removed from the polymer cement by
contacting with an excess of 1% by weight aqueous sulfuric acid
solution (organic/aqueous=1/3(vol/vol)). The organic phase was
washed repeatedly with water to remove excess sulfuric acid.
Ammonia gas was bubbled through the organic phase to ensure
complete neutralization. An antioxidant, Irganox 1076, was added to
the cement in an amount to afford a concentration of 0.1% by weight
in the final product. The solvent was removed from the polymer
under vacuum affording a clear, low viscosity liquid, hydrogenated
butadiene polymer having about two terminal hydroxyl groups per
molecule. The properties of this sample are listed in Tables 1 and
2 which follow the description of Examples 2-5 below. Several
commercial hydrogenated polybutadiene diols are included for
comparison.
EXAMPLES 2-5
The procedure of Example 1 was modified to prepare a series of
hydrogenated butadiene polymers having about two terminal hydroxyl
groups per molecule, different peak molecular weights, and
different amounts of 1,2-addition. The molecular weight of the diol
was adjusted by varying the diinitiator to monomer ratio during
polymerization of the butadiene. The 1,2-addition was varied by
adjusting the diethyl ether content of the solvent before
polymerization and by adjusting the temperature at which the
butadiene polymerization was conducted. Higher levels of
1,2-addition were favored by higher levels of diethyl ether and
lower reaction temperatures. Synthesis in this way afforded
products with the structures of Table 1 and properties of Table
2.
TABLE-US-00001 TABLE 1 1,2- EO Capping Hydro- Example MW Addition
Efficiency genation Number (Peak) (%) (%) (%) 1 2900 40 82 95 2
3900 41 95 98 3 5060 40 92 99 4 3500 52 87 98 5 3970 48 85 99
POLYTAIL HA.sup.1 2300 84 NA .sup. 99.sup.3 NISSO GI-2000.sup.2
2380 84 NA .sup. 98.sup.3 POLYTAIL H.sup.1 3720 22 NA NA
.sup.1Polymer produced by Mitsubishi. .sup.2Polymer produced by
Nippon Soda. .sup.3Measured by ozonolysis.
TABLE-US-00002 TABLE 2 1,2- Adj. Example MW Addition Viscosity
Viscosity Number (Peak) (%) (poise) (poise/MW.sup.3,4) 1 2900 40
155 0.26 .times. 10.sup.-9 2 3900 41 836 0.52 .times. 10.sup.-9 3
5060 40 2322 0.59 .times. 10.sup.-9 4 3500 52 353 0.32 .times.
10.sup.-9 5 3970 48 760 0.44 .times. 10.sup.-9 POLYTAIL HA.sup.1
2300 84 1650 6.1 .times. 10.sup.-9 NISSO GI-2000.sup.2 2380 84 1480
4.9 .times. 10.sup.-9 POLYTAIL H.sup.1 3720 22 Solid.sup.3 --
.sup.1Polymer produced by Mitsubishi. .sup.2Polymer produced by
Nippon Soda. .sup.3Infinite viscosity at room temperature.
The relationship between viscosity and 1,2-addition for the
hydrogenated butadiene polymers is plotted in FIG. 1 wherein the
viscosity data is adjusted to remove molecular weight variations as
described above.
For many applications such as coatings it is desirable to have
polymers that have terminal functional groups and have low
viscosity at room temperature to allow application without any
solvent, preferably at the highest possible solids content. While
it is known in the art that hydrogenated butadiene polymers having
less than 30% 1,2-addition are crystalline solids, Table 2 and FIG.
1 show that 1,2-addition between 30 and 70% provides surprisingly
low viscosities at room temperature for hydrogenated butadiene
polymers having terminal groups. The polymers of the invention
preferably have a ratio of viscosity (poise) to peak molecular
weight raised to the 3.4 power of at most 2.0.times.10.sup.-9, most
preferably less than 1.0.times.10.sup.-9.
Results for Examples 2 and 3 validate the theoretical relationship
between viscosity and peak molecular weight. The ratios of
viscosity to peak molecular weight raised to the 3.4 power for
Examples 2 and 3 are almost identical although the polymers have
significantly different molecular weights and significantly
different viscosities.
EXAMPLE 6 (HYPOTHETICAL)
A hydrogenated butadiene polymer having terminal hydroxyl groups is
prepared as described in Example 1 except that the ratio of
diinitiator to butadiene monomer is adjusted to provide a peak
molecular weight of 10000.
EXAMPLE 7 (HYPOTHETICAL)
A hydrogenated butadiene polymer having terminal hydroxyl groups is
prepared as described in Example 1 except that the ratio of
diinitiator to butadiene monomer is adjusted to provide a peak
molecular weight of 16000.
EXAMPLE 8 (HYPOTHETICAL)
A linear, hydrogenated butadiene polymer having a peak molecular
weight of 4000, about two terminal carboxyl groups per molecule,
and 1,2-addition of 50% is produced by the procedure of Example 1
with the following modifications.
Polymerization is conducted at 15.degree. C. with 10% diethyl ether
to obtain 50% 1,2-addition.
The precursor butadiene polymer having terminal lithium atoms is
carboxylated by pumping the polymer solution through a pipeline
reactor wherein the solution is contacted in a static mixer with
high pressure carbon dioxide. Efficient mixing and high pressure
minimize coupling of polymer molecules.
The carboxylated polymer can be hydrogenated by the procedure of
Example 1 if a large excess of the nickel catalyst is used to
overcome reduced activity caused by the carboxyl groups. The
carboxylated polymer is preferably hydrogenated after
esterification of the carboxylate groups with methanol and an acid
catalyst as described in U.S. Pat. No. 5,002,676. After
hydrogenation, the ester groups are converted back to carboxylate
groups by washing with a mixture a sulfuric acid/water which also
removes the hydrogenation catalyst.
EXAMPLE 9 (HYPOTHETICAL)
A linear, hydrogenated butadiene polymer having a peak molecular
weight of 4000, about two terminal amine groups per molecule, and
1,2-addition of 50% is produced by the procedure of Example 1 with
the following modifications.
Polymerization is conducted at 15.degree. C. with 10% diethyl ether
to obtain 50% 1,2-addition.
The precursor butadiene polymer having terminal lithium atoms is
aminated by a ring opening reaction with a diaziridine,
1,5-diazabicyclo[3.1.0]hexane as described in U.S. Pat. No.
4,753,991 which is incorporated by reference herein. The polymer is
hydrolyzed by treatment with an excess of acetic acid (2 hours,
90.degree. C.) and recovered by coagulation in methanol.
Before hydrogenation, the amine terminated polymer is reacted in
cyclohexane with a slight excess of acetyl chloride (using pyridine
as a promoter) to exhaustively acylate the amine groups to amide
groups. The amide groups are returned to amine groups during
catalyst extraction with aqueous sulfuric acid.
EXAMPLE 10 (HYPOTHETICAL)
A 1000 ml four neck flask is fitted with a mechanical stirrer, a pH
probe, an aqueous caustic inlet tube, and a Claisen adapter to
which there is attached a dry ice condenser and a gas inlet tube.
The flask is charged with 400 ml of water, 500 ml of methylene
chloride, 1.0 ml of triethylamine, 2.0 g (0.0133 moles for 3.3
molar percent) of p-tertiarybutylphenol, 5.0 g (0.0014 moles) of
the hydrogenated butadiene polymer of Example 5, and 91.3 g (0.40
moles) of bisphenol-A. With stirring, phosgene is introduced into
the flask at a rate of 1 g/min for 50 minutes with the pH
maintained in a range of 10.5 to 11.5 by addition of 50% aqueous
sodium hydroxide. The resin layer is then separated from the brine
layer, washed with 3 wt% aqueous HCl until washing remains acidic,
then twice washed with distilled water. The resin is then
precipitated into methanol in a Waring blender and washed with
methanol. The resin is useful as a molding resin to prepare
exterior components of automobiles.
EXAMPLE 11 (HYPOTHETICAL)
Example 10 is repeated by replacing the hydrogenated butadiene
polymer of Example 5 with 5.0 g (0.0005 moles) of the hydrogenated
butadiene polymer of Example 6.
EXAMPLE 12 (HYPOTHETICAL)
Example 10 is repeated by replacing the hydrogenated butadiene
polymer of example 5 with 5.0 g (0.0003 moles) of the hydrogenated
butadiene polymer of Example 7.
EXAMPLE 13 (HYPOTHETICAL)
A 1000 ml four neck flask is fitted with a mechanical stirrer, a pH
probe, an aqueous caustic inlet tube, and a Claisen adapter to
which there is attached a dry ice condenser and a gas inlet tube.
The flask is charged with 400 ml of water, 550 ml of methylene
chloride, 0.5 ml of triethylamine, 5.5 g (0.0016 moles) of the
hydrogenated butadiene polymer of Example 5, and 65 g (0.285 moles)
of bisphenol-A. With stirring, phosgene is introduced into the
flask at a rate of 0.75 g/min for 36 minutes with the pH maintained
in a range of 10.5 to 11.7 by addition of 50% aqueous sodium
hydroxide. The resin layer is then separated and washed as
described in Example 10 from the brine layer, washed with 3 wt%
aqueous HCl until washing remains acidic, then twice washed with
distilled water. The resin is then precipitated into methanol in a
Waring blender and washed with methanol. The resin is useful as a
molding resin to prepare gaskets.
EXAMPLE 14 (HYPOTHETICAL)
Example 13 is repeated by replacing the hydrogenated butadiene
polymer of Example 5 with 5.5 g (0.00055 moles) of the hydrogenated
butadiene polymer of Example 6.
EXAMPLE 15 (HYPOTHETICAL)
Example 13 is repeated by replacing the hydrogenated butadiene
polymer of Example 5 with 5.5 g (0.0003 moles) of the hydrogenated
butadiene polymer of Example 7.
EXAMPLE 16 (HYPOTHETICAL)
A 1000 ml four neck flask is fitted with a mechanical stirrer, a pH
probe, an aqueous caustic inlet tube, and a Claisen adapter to
which there is attached a dry ice condenser and a gas inlet tube.
The flask is charged with 400 ml of water, 500 ml of methylene
chloride, 3.0 ml of triethylamine, 0.65 g (0.004 moles) of
p-tertiary-butyl-phenol, 40.0 g (0.011 moles) of the hydrogenated
butadiene polymer of Example 5, 30 g (0.131 moles) of bisphenol-A,
and 45 g (0.083 moles) of tetrabromo-bis-phenol-A. With stirring,
phosgene is introduced into the flask at a rate of 1 g/min for 5
minutes at an initial pH of from 8.0 to 9.0. Then phosgenation is
continued for an additional 21 minutes while maintaining the pH
within the range of 10.5 to 11.5 by addition of 50% aqueous sodium
hydroxide. The resin layer is then separated from the brine layer,
washed with 3 wt % aqueous HCl until washing remains acidic, then
twice washed with distilled water. The resin is then precipitated
into methanol in a Waring blender and washed with methanol. The
resin is useful for extruding radio-opaque tubing for use as venous
catheters.
EXAMPLE 17 (HYPOTHETICAL)
Example 16 is repeated by replacing the hydrogenated butadiene
polymer of Example 5 with 40.0 g (0.004 moles) of the hydrogenated
butadiene polymer of Example 6.
EXAMPLE 18 (HYPOTHETICAL)
Example 16 is repeated by replacing the hydrogenated butadiene
polymer of Example 5 with 40.0 g (0.0025 moles) of the butadiene
polymer of Example 7.
EXAMPLE 19 (HYPOTHETICAL)
A polyamide-hydrogenated butadiene block copolymer is produced by
reacting 945.7 g (8.31 moles) of caprolactam, 4.3 g (0.029 moles)
of adipic acid, and 50 g (0.0145 moles) of the hydrogenated
butadiene polymer of Example 5 in a 2 liter stainless steel reactor
in the presence of 1 g of catalyst (85% by weight phosphoric acid
in water) at 200.degree. C. and a stirring speed of 200 rpm. After
two hours of reaction, the reaction temperature is raised to
260.degree. C. and a vacuum (0.5 mm Hg) was applied for two hours.
The resulting resin is useful as a molding composition to prepare
exterior automotive components.
EXAMPLE 20 (HYPOTHETICAL)
A polyamide-hydrogenated butadiene block copolymer is produced by
the process of Example 19 except that the reactants are varied to
include 674.2 g of the caprolactam, 25.8 g of the adipic acid, and
300 g of the hydrogenated butadiene polymer of Example 6.
EXAMPLE 21 (HYPOTHETICAL)
A polyamide-hydrogenated butadiene block copolymer is produced by
the process of Example 19 except that the reactants are varied to
include 348.5 g of the caprolactam, 51.5 g of the adipic acid, and
600 g of the hydrogenated butadiene polymer of Example 7.
EXAMPLE 22 (HYPOTHETICAL)
A polyamide-hydrogenated butadiene block copolymer is produced by
reacting 948.5 g of caprolactam, 1.5 g of adipic acid, and 50 g of
the hydrogenated butadiene polymer of Example 5 in a 2 liter
stainless steel reactor in the presence of 1 g of catalyst (85% by
weight phosphoric acid in water) at 200.degree. C. and a stirring
speed of 200 rpm. After two hours of reaction, the reaction
temperature is raised to 260.degree. C. and a vacuum (0.5 mm Hg)
was applied for two hours. The resulting resin is useful as a
molding composition to prepare exterior automotive components.
EXAMPLE 23 (HYPOTHETICAL)
A polyamide-hydrogenated butadiene block copolymer is produced by
the process of Example 22 except that the reactants are varied to
include 691.2 g of the caprolactam, 8.8 g of the adipic acid, and
300 g of the hydrogenated butadiene of Example 6.
EXAMPLE 24 (HYPOTHETICAL)
A polyamide-hydrogenated butadiene block copolymer is produced by
the process of Example 22 except that the reactants are varied to
include 382.5 g of the caprolactam, 17.5 g of the adipic acid, and
600 g of the hydrogenated butadiene polymer of Example 7.
EXAMPLE 25 (HYPOTHETICAL)
A polyamide-hydrogenated butadiene block copolymer is produced by
reacting 949.1 g of caprolactam, 0.9 g of adipic acid, and 50 g of
the hydrogenated butadiene polymer of Example 5 in a 2 liter
stainless steel reactor in the presence of 1 g of catalyst (85% by
weight phosphoric acid in water) at 200.degree. C. and a stirring
speed of 200 RPM. After two hours of reaction, the reaction
temperature is raised to 260.degree. C. and a vacuum (0.5 mm Hg)
was applied for two hours. The resulting resin is useful as a
molding composition to prepare exterior automotive components.
EXAMPLE 26 (HYPOTHETICAL)
A polyamide-hydrogenated butadiene block copolymer is produced by
the process of Example 25 except that the reactants are varied to
include 694.5 g of the caprolactam, 5.5 g of the adipic acid, and
300 g of the hydrogenated butadiene of Example 6.
EXAMPLE 27 (HYPOTHETICAL)
A polyamide-hydrogenated butadiene block copolymer is produced by
the process of Example 25 except that the reactants are varied to
include 389.0 g of the caprolactam, 11.0 g of the adipic acid, and
600 g of the hydrogenated butadiene of Example 7.
EXAMPLE 28 (HYPOTHETICAL)
A polyamide-hydrogenated butadiene block copolymer is produced by
refluxing 419.7 g (3.62 moles) of hexamethylene diamine, 530.3 g
(3.62 moles) of adipic acid, and 50 g (0.0145 moles) of the
hydrogenated butadiene polymer of Example 5 in a resin kettle at a
temperature between 120.degree. to 150.degree. C. for 3 hours under
a nitrogen blanket. The mixture is then gradually heated from
reflux temperature to 200.degree. C. while water is removed by
distillation. Six drops of phosphoric acid are added, and the
mixture is heated at 220.degree. to 240.degree. C. under a vacuum
of 0.05 to 5 mm Hg for 3 hours. The resulting copolymer is allowed
to cool to room temperature. The resin is useful as a component for
exterior automotive applications.
EXAMPLE 29 (HYPOTHETICAL)
A polyamide-hydrogenated butadiene block copolymer is produced by
the process of Example 28 except that the reactants are varied to
include 350.4 g of the hexamethylene diamine, 449.5 g of the adipic
acid, and 200 g of the hydrogenated butadiene polymer of Example
5.
EXAMPLE 30 (HYPOTHETICAL)
A polyamide-hydrogenated butadiene block copolymer is produced by
refluxing 420.3 g of hexamethylene diamine, 529.7 g of adipic acid,
and 50 g of the hydrogenated butadiene polymer of Example 6 in a
resin kettle at a temperature between 120 to 150.degree. C. for 3
hours under a nitrogen blanket. The mixture is then gradually
heated from reflux temperature to 200.degree. C. while water is
removed by distillation. Six drops of phosphoric acid are added,
and the mixture is heated at 220.degree. to 240.degree. C. under a
vacuum of 0.05 to 5 mm Hg for 3 hours. The resulting copolymer is
allowed to cool to room temperature. The resin is useful as a
component for exterior automotive applications.
EXAMPLE 31 (HYPOTHETICAL)
A polyamide-hydrogenated butadiene block copolymer is produced by
the process of Example 30 except that the reactants are varied to
include 352.9 g of the hexamethylene diamine, 447.1 g of the adipic
acid, and 200 g of the hydrogenated butadiene polymer of Example
6.
EXAMPLE 32 (HYPOTHETICAL)
A polyamide-hydrogenated butadiene block copolymer is produced by
refluxing 420.4 g of hexamethylene diamine, 529.6 g of adipic acid,
and 50 g of the hydrogenated butadiene polymer of Example 7 in a
resin kettle at a temperature between 120.degree. to 150.degree. C.
for 3 hours under a nitrogen blanket. The mixture is then gradually
heated from reflux temperature to 200.degree. C. while water is
removed by distillation. Six drops of phosphoric acid are added,
and the mixture is heated at 220.degree. to 240.degree. C. under a
vacuum of 0.05 to 5 mm Hg for 3 hours. The resulting copolymer is
allowed to cool to room temperature. The resin is useful as a
component for exterior automotive applications.
EXAMPLE 33 (HYPOTHETICAL)
A polyamide-hydrogenated butadiene block copolymer is produced by
the process of Example 32 except that the reactants are varied to
include 353.4 g of the hexamethylene diamine, 446.6 g of the adipic
acid, and 200 g of the hydrogenated butadiene polymer of Example
7.
EXAMPLE 34 (HYPOTHETICAL)
A polyester-hydrogenated butadiene block copolymer is produced by
charging into a 1 liter reaction kettle 45.0 g of 1,4-butanediol,
3.8 g of the hydrogenated butadiene polymer of Example 7, 48.5 g of
dimethyl terephthalate, 0.129 g of titanium butoxide, and 0.129 g
of Irganox 1098, an antioxidant. Transesterification of the
reactants is carried out at 180.degree. C. for 2.5 hours under a
nitrogen blanket. The methanol released by the reaction is
collected in a condenser. The temperature is then raised to
245.degree. C. to start polymerization. Vacuum is applied slowly
over a 15 minute period to 0.15 mm Hg. About one-half of the
1,4-butanediol is distilled off and then polymerization is
continued for 3 hours. The resulting polymer is useful as a molding
compound for exterior automotive components.
EXAMPLE 35 (HYPOTHETICAL)
A polyester-hydrogenated butadiene block copolymer is produced by
the process of Example 34 except that the reactants are modified to
contain 30.6 g of the hydrogenated butadiene polymer of Example
5.
EXAMPLE 36 (HYPOTHETICAL)
A polyester-hydrogenated butadiene block copolymer is produced by
the process of Example 34 except that the reactants are modified to
contain 107.3 g of the hydrogenated butadiene polymer of Example
5.
EXAMPLE 37 (HYPOTHETICAL)
A polyester-hydrogenated butadiene block copolymer is produced by
charging into a 1 liter reaction kettle 45.0 g of 1,3-propanediol,
3.6 g of the hydrogenated butadiene polymer of Example 5, 48.5 g of
dimethyl terephthalate, 0.129 g of titanium butoxide, and 0.129 g
of Irganox 1098, an antioxidant. Transesterification of the
reactants is carried out at 180.degree. C. for 2.5 hours under a
nitrogen blanket. The methanol released by the reaction is
collected in a condenser. The temperature is then raised to
245.degree. C. to start polymerization. Vacuum is applied slowly
over a 15 minute period to 0.15 mm Hg. About one-half of the
1,3-propanediol is distilled off and then polymerization is
continued for 3 hours. The resulting polymer is useful as a molding
compound for exterior automotive components.
EXAMPLE 38 (HYPOTHETICAL)
A polyester-hydrogenated butadiene block copolymer is produced by
the process of Example 37 except that the reactants are modified to
contain 28.9 g of the hydrogenated butadiene polymer of Example
5.
EXAMPLE 39 (HYPOTHETICAL)
A polyester-hydrogenated butadiene block copolymer is produced by
the process of Example 37 except that the reactants are modified to
contain 101.3 g of the hydrogenated butadiene polymer of Example
5.
EXAMPLE 40 (HYPOTHETICAL)
A polyester-hydrogenated butadiene block copolymer is produced by
charging into a 1 liter reaction kettle 31.0 g of 1,2-ethanediol,
3.4 g of the hydrogenated butadiene of Example 5, 48.5 g of
dimethyl terephthalate, 0.129 g of titanium butoxide, and 0.129 g
of Irganox 1098, an antioxidant. Transesterification of the
reactants is carried out at 180.degree. C. for 2.5 hours under a
nitrogen blanket. The methanol released by the reaction is
collected in a condenser. The temperature is then raised to
245.degree. C. to start polymerization. Vacuum is applied slowly
over a 15 minute period to 0.15 mm Hg. About one-half of the
1,2-ethanediol is distilled off and then polymerization is
continued for 3 hours. The resulting polymer is useful as a molding
compound for exterior automotive components.
EXAMPLE 41 (HYPOTHETICAL)
A polyester-hydrogenated butadiene block copolymer is produced by
the process of Example 40 except that the reactants are modified to
contain 27.4 g of the hydrogenated butadiene polymer of Example
5.
EXAMPLE 42 (HYPOTHETICAL)
A polyester-hydrogenated butadiene block copolymer is produced by
the process of Example 40 except that the reactants are modified to
contain 96.0 g of the hydrogenated butadiene polymer of Example
5.
EXAMPLE 43
A polyurethane coating was prepared by placing 54.1 parts by weight
(pbw) of the hydroxyl terminated, hydrogenated polybutadiene diol
of Example 3, 0.01 pbw of dibutyl tin dilaurate and 36.0 pbw of
toluene into a jar. The jar was capped and placed on a shaker for
30 minutes. Then 9.9 pbw of the isocyanate DESMODURZ-4370 (ex.
Miles) were added to the jar and the jar was returned to the shaker
for 30 minutes. This mixture was applied with a paint brush to a
steel panel. After drying/curing for 2 weeks at room temperature,
the coated film was useful as a clear, elastomeric, polyurethane
coating.
EXAMPLE 44
A polyurethane coating was prepared by placing 33.6 pbw of the
hydrogenated polybutadiene diol of Example 3, 0.004 pbw of dibutyl
tin dilaurate, 22.4 pbw of toluene, and 37.9 pbw of the titanium
dioxide TI-PURE R-902 (ex. DuPont) into a jar. Grinding grit was
then added to the jar. This mixture was rolled on a bottle roller
until the TiO.sub.2 particle size was reduced to a Hegman 6
"fineness of grind". This took about 3 days of rolling the jar. The
blend was filtered to remove the grinding grit. To 93.9 pbw of this
blend was added 6.1 pbw of the isocyanate DESMODUR Z-4370. After
thoroughly mixing in the isocyanate, the mixture was applied with a
10 mil doctor blade onto a steel panel. After drying/curing for 2
weeks at room temperature, the coated film was useful as a white,
elastomeric, polyurethane coating.
EXAMPLE 45 (HYPOTHETICAL)
An isocyanate terminated prepolymer is prepared by placing 44.3 pbw
of the hydrogenated polybutadiene diol of Example 5, 5.7 pbw of a
diphenyl methane diisocyanate (2/1 NCO/OH), and 50 pbw of toluene
into a jar and gently rolling the jar for 2 weeks at room
temperature. Then 100 pbw of this prepolymer is mixed with 50 pbw
of WINGTACK 95 hydrocarbon tackifying resin (ex. Goodyear) and 100
pbw of ATOMITE calcium carbonate (ex. Thompson Weiman) in a sigma
blade mixer under a dry nitrogen blanket. The material is then
packaged with critical exclusion of moisture until the package is
opened for use. The material is useful as a moisture-curable,
polyurethane/urea sealant, caulk, or coating.
EXAMPLE 46 (HYPOTHETICAL)
An acrylate terminated prepolymer is prepared by placing 3.5 pbw of
hydroxy ethyl acrylate, 6.7 pbw isophorone diisocyanate (2/1
NCO/OH), 0.007 pbw dibutyl tin dilaurate, and 30 pbw xylene into a
resin kettle. With gentle stirring, this mixture is heated to
80.degree. C. and held for 3 hours. Then 59.8 pbw of the
hydrogenated polybutadiene diol from Example 5 is added and heating
is continued for another 3 hours at 80.degree. C. to give the
acrylate terminated prepolymer. This material is useful in
coatings, sealants and adhesives which are cured by free radical
processes, initiated for example by peroxides or radiation.
EXAMPLE 47 (HYPOTHETICAL)
A water-borne polyurethane/urea dispersion is prepared by charging
53.1 pbw of the hydrogenated polybutadiene diol of Example 5, 14.0
pbw of the isocyanate DESMODUR W (ex. Miles), 3.5 pbw of dimethylol
propionic acid, and 23.6 pbw of xylene to a resin kettle. This
mixture is heated to 80.degree. C. and is held for 4 hours to
prepare the isocyanate terminated prepolymer. Then 2.7 pbw of
triethyl amine is added to ionize the acid groups and heating is
continued for another hour. This product is then dispersed in 290
pbw of water and 3.1 pbw of DYTEK A is quickly added. Heating at
80.degree. C. is continued for another hour to chain extend the
prepolymer giving the water-borne polyurethane/urea dispersion.
This material is useful as a low VOC coating.
EXAMPLE 48 (HYPOTHETICAL)
A bake-cured coating was prepared by mixing 40 pbw of the
hydrogenated polybutadiene diol of Example 3, 9 pbw CYMEL 303
hexamethoxy melamine resin (ex. American Cyanamid), 1 pbw of CYCAT
600 acid catalyst (ex. American Cyanamid), and 50 pbw of toluene in
a jar on a bottle roller overnight. Coatings about 2 mils thick
were cast on polyester film with a 10 mil doctor blade. The
coatings are cured for 10, 20, or 30 minutes in an oven at
150.degree. C. Gel contents measured on these films were 81%, 84%,
and 92%, respectively. (Gel content is the percentage of material
in the coating which is insoluble in toluene after the coating is
baked.) These compositions should be useful in amino resin cured
coatings.
EXAMPLE 49 (HYPOTHETICAL)
A saturated polyester resin (1.3/1 OH/COOH) is prepared by charging
55.5 g of the hydrogenated butadiene diol of Example 3, 102.3 g of
neopentyl glycol, 9.9 g of trimethylol propane, 70.4 g of
isophthalic acid, 61.9 g of adipic acid, 0.40 g of dibutyl tin
dilaurate, and 30 g of xylene to a 500 ml resin kettle equipped
with a stirrer and a partial condenser. The ingredients are
carefully heated to 230.degree. C. under a nitrogen purge. The
esterification reaction is continued at 230.degree. C. for 6 hours.
After cooling to room temperature, the product is a sticky, opaque
mass. The product is useful as a toughened, high solids, hydroxyl
terminated, polyester resin for coatings.
* * * * *