Note: Descriptions are shown in the official language in which they were submitted.
wo so/os364 Pcr/usso/00034
VINYLOXY HYDRO~YALKX~CY~
AND PRE~E~5~L THE~EEQ~
BACKGROUND OF THE INV~ION
This invention relates to compounds having a
vinyl group and a hydro~yl group as terminal groups of the
compound. More particularly, this invention relates to
monomers which possess a vinyl ether substituent and a
hydrosyl substituent.
Urethane polymers have had great commercial
success when used as protective coatings, films and
adhesives. The genesis for these polymers is usually a
monomer having both an acrylic functional group and a
hydro~yl functional qroup. In the process for making a
protective coating or film the hydroxyl group is converted
to a urethane group by reaction with an isocyanate. The
resulting acrylic urethane monomer is then applied to a
surface and cured thereon by radiation. However, this
process for producing urethane coatings and films has many
shortcomings.
Since the polymerization and curing of acrylic
functional groups proceeds by a free radical mechanism,
polymerization and curing must be carried out in the
absence of air, a known free radical inhibitor. The
osygen free atmosphere can be achieved by effecting the
polymerization under a blanket of nitrogen; however this
requirement greatly increases the cost of the process.
Another disadvantage in the preparation of
acrylic urethane coatings is that a curing rate
sufficiently high to meet certain requirements such as
coatings for automotive fascia, etc., are not achievable
~y radiation esposure. Finally, it is found that urethane
coatings made from acrylic urethane monomers have poor
adhesion to hard, smooth surfaces such as metal or glass.
wogo/09364 Pcr/usgo/0~034
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It is therefore an object of this invention to
provide a compound which can be converted to a urethane
monomer having a high radiation cure rate in the absence
or presence of air to produce a coating of e~cellent
adherence to hard surfaces such as qlass or metal.
Another object is to provide an economical and
commercially feasible process for the manufacture of the
present compounds.
Still another object is to provide a substrate
coated with the present compound which possesses superior
stability.
These and other objects of the invention will
become apparent from the following description and
disclosure.
THE INVENTION
In accordance with this invention, there is
provided a vinylo~y hydro~yalkyl cycloalkane compound
having the structure
HO(CH2)s-A-(CH2)~,0CH=CH2
wherein ~ has a value of from 1 to 10; x' has a value of
from 0 to 10 and A is a cycloalkylene group having from 3
to 8 carbon atoms in the ring and is optionally
substituted with lower alkyl. Preferred of this group are
those compounds wherein s and ~' each have a value of from
1 to 4 and, most preferably, where A is cyclohe~ylene.
WO90/09~ PCT/US90/00~
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The compounds of this invention are useful
chemical intermediates. For example, these products can
be polymerized to branched structures having repeating
units of
(CH-CH2)n~
t CH2 ) ~ A- ( CH2 ) SOH
The polymer chains, in turn, can be cross-linked at the
terminal hydroxy group by condensation, by dehydration or
by reaction with polyols, such as diols, to form the
corresponding ethers. Additionally, they can be reacted
with diacids, both aliphatic and aromatic dicarboxylic
acids, to form the corresponding esters. These polymers,
because of branching and~or cross-linking provide coatings
which are more resistant to chemical attack and abrasion
than linear types and are adapted to curing by irradiation
at a reasonably high rate. Also, the polymers provide a
harder more durable surface on the substrate after curing
than the linear polymerized products. A major advantage
of the present products is their ability to be converted
to vinyl ether urethanes by reaction with an isocyanate,
e.g. according to the equation:
2Ho(cH2)x-A-(cH2)x,ocH=cH2 + C6H4(NCO)
O; O
CH2 CHO~CH2)x,-A-~CH2)xoc_HN ~ NH-eo(cH2)x-A-(cH2)xlocH=cH2
W090/09~ PCT/US90/000~
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These urethanes polymerize and are rapidly cured by a
cationic mechanism activated by radiation, e.g. from W
light or an electron beam source, to form hard, durable
coatings; thus eliminating the need for formation under a
blanket of nitrogen which is required by free radical
polyrnerization and curing.
It is readily apparent that the present compounds
can also be employed as monomers in copolymerizations with
other monomers selected from the groups consisting of
olefinic compounds, maleic anhydride, vinyl pyrrolidone,
acrylics, methacrylics, etc. The products in their
non-polymerized state are also useful in the formation of
many non-polymeric compounds through condensation,
dehydration, esterification, substitution at the hydroxy
site or addition to the terminal vinyl group; thus
providing useful multifunctional reaction intermediates.
The present products are readily synthesized by
reacting a diol corresponding to the formula
~0(CH2),C-A-(CH2),~,O~l
with acetylene. Ezamples of suitable diols include
1,4-di~hydro~ymethyl~ cyclohe2ane; 1,5-di(hydrosydecyl)
cyclooctane; 1,3-di(hydroxyethyl) ethylcyclopentane;
4(4-hydrosycyclohe~yl) butanol;
(3-hydro~y)-2,5-dimethyl-cyclooctyl decanol; etc. In this
reaction the mole ratio of diol to acetylene can vary
between about 1:1 and about 1:1.5. At low reaction
pressure, the acetylene can be introduced into the
reaction zone without dilution; however, at elevated
pressures, it is recommended that an inert non-ozygen
containing gaseous diluent such as nitrogen, a Cl-C3
wo so/os364 Pcr/ussl)/00034
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alkane or helium be used to dilute the acetylene
reactant. When the diluent is employed, acetylene
concentration as low as 10~ can be used although between
about 40 and about 60 wt. % acetylene in diluent is most
preferred.
The above reaction is carried out in an osygen
free atmosphere which is generally achieved by purging
with nitrogen and is effected in the presence of a basic
catalyst such-as an alkali metal hydroside, e.g. potassium
hydroside, or sodium hydroside as potassium alkoside or an
amine. The concentration of catalyst employed can range
from about 0.1% to about 5% by weight.
The process is effected at a temperature of
between about 120C. and about 200C. under from about 10
to about 200 psig. in a period of from about 2 to about 20
hours reaction time. Preferred conditions include a
temperature of between about 140C. and about 170C.,
under between about S0 and about 100 psig. for a period of
from about 4 to about 8 hours.
~ aving thus generally described the invention,
reference is now had to the following esamples which
illustrate preferred embodiments but which are not to be
construed as limiting to the scope of the invention as
more broadly set forth above and in the appended claims.
EXAMPL~I
Molten 1,4-bis-(hydrosymethyl) cyclohesane
(1802.6 grams) and 36 grams of potassium hydroside pellets
(85%) were charged with a one gallon autoclave. The
autoclave was purged three times with nitrogen, then
evacuated to 10 mm of mercury pressure and heated at 90C.
for 30 minutes to remove water of reaction.
WO90/09~ f~ J - 6 - PCT/US90/~00~
Propane gas was introduced into the autoclave to
60 psi and the autoclave heated to 160C. Additional
propane gas was added at 160C. until the pressure reached
100 psi. Acetylene was then introduced until a total
pressure of 200 psi was achieved. After 6.5 hours at 200
psi and 160C. the autoclave was cooled to room
temperature, purged 3 times with nitrogen, and its
contents discharged.
The crude product (1,816 g.) was distilled under
vacuum (1 mm Hg) using a 15 plate Oldershaw column, and a
clear water white fraction boiling between 95C. and
110C. was collected. The fraction boiling at 102C.
weighed 263 grams and was identified as 99.3% pure
monovinyl ether of 1,4-bis-hydrosymethyl cyclohesane by
nmr, using CD C13 solvent.
For esample, Ezample 1 was repeated except that
1,5-bis-(hydrozyethyl) cyclooctane is substituted for
1,4-bis-(hydrozymethyl) cyclohesane. The divinyl ether
product is recovered in greater than 90% yield.
