Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
207~31J 7
WO91/13052 PCT/US91/00639
--1--
VINYL ETHER COMPOUNDS
Alkenyl ether carbonates having the formula
11
A-OCO(B)nOCH=CHR tA)
wherein A is RHC=CHO(B)n-, lower alkyl or a mixture
thereof; ~ is a divalent radical having from 2 to 12 carbon
atoms and is selected from the group of alkylene, mono or
polyalkoxylated alkylene, alken~lene, alkynylene, arylene,
alkarylene and aralkylene radicals, which radicals are
optionally substituted with halo, alkyl, cyano, nitro or
alkoxy; R is hydrogen or lower alkyl and n has a value of
from 1 to 10.
Preferred species of these alkenyl ether
carbonates are those wherein n has a value of one and A is
RHC=CHO(B)n-, where B is butylene or dimethylene
cyclohexane or A is methyl or ethyl and B is butylene.
Most preferred of this group are those wherein R is
hydrogen.
There is also provided alkenyl ether
polycarbonates having the formula
o O
A-OCO[R"(OR")mOCO]nROCH=CHR' (B)
wherein A is R'HC=CHOR-, lower alkyl or a mixture thereof;
R and R" are each independently a divalent radical having
from 2 to 20 carbon atoms and are selected from the group
of alkylene, mono- or poly- alkoxylated alkylene,
alkenylene, alkynylene, arylene, alXarylene and aralkylene
radicals, which radicals are optionally substituted with
halo, alkyl, cyano, nitro or alkoxy; R' is hydrogen or
lower alkyl; (n) has a value of from 1 to 10 and (m) has a
value of from 0 to 10; with the proviso that R" contains at
least 3 carbon atoms when m is zero.
20~S3~7
W091/1~2 PCT/US91/~
2 --
Preferred species of the present alkenyl ether
polycarbonates are those wherein R' is hydrogen and A is
R'HC=CHOR- or -CH3; R is C2 to C8 alkylene; R" is
C2 to C6 alkylene; m has a value of from 0 to 6 when R"
contains at least 3 carbon atoms and m has a value of from
l to 6 when R" contains 2 carbon atoms.
Also provided is a polymerizable compound having
the formula
~ O-
R'HC=CHO(B)m-OCO- R"(OH)n-b (C)
b
which is the reaction product-:of a p~ly~ydroxylated
reactant (I) having the formula ROH and a dialkenyloxy
carbonate coreactant (II) having the formula:
R'HC=CHO(B)mOCO(B)mOCH=CHR'
wherein R is a C3 to C50 saturated or
unsaturated, linear, branched or cyclic polyhydroxylated
hydrocarbon radical optionally substituted with halo,
alkoxy, lower alkyl, cyano or nitro;
R' is hydrogen or lower alkyl
R" is the same as R except that it contains at
least one less hydroxy group.
B is a linear, branched or cyclic divalent radical
having from 2 to 12 carbon atoms and is selected from the
group of alkylene, mono- or poly- alkoxylated alkylene,
.: ,
2Q7~3~7
WO91/13052 PCT/US9l/0~39
-- 3
alkenylene, alkynylene, arylene, alkarylene and aralkylene
radicals, which radicals ar~ optionally substituted with
halo, lower alkyl, cyano, nitro or alkoxy (m) has a value
of from 1 to 10; (b) has a value of from at least 1 up to
the number of hydroxy groups in ROH and (n) represents the
number of hydroxy groups in ROH, generally from 3 to 10
hydroxy groups.
Polyhydroxylated reactant (I) contains at least 3,
preferably not more than 10, hydroxy ~roups and includes
hydroxylated derivatives of alkylene, alkenylene,
alkynylene, arylene, alkarylene, aralkylene and ethoxylated
or propoxylated species of these radicals. Specific
examples of hydroxylated reactant (I) are represented by
trihydroxy benzene, trihydroxy nitrDhen2ene, tetrahydroxy
diphenyl dimethyl methane, hexahydroxy diphenyl methane,
tetrahydroxy styrene, tetrahydroxy--tolu~ne,
dichlorotrihydroxy benzene, trihydroxy cyanomethyl benzene,
dinitrotrihydroxybenzene, hexahydroxy anthranol, and
alkoxylated derivatives thereof 1,2,5,7,9-penta-
hydroxynonane, 1,2,4-trihydroxybutane,
4,5-dichloro-1,3,6,10-tetrahydroxydecane, decahydroxy
tetracosane, decahydroxy pentacontane,
1,2,11,12-tetrahydroxy dodec-6-yne,
3,5-bromo-1,2,13,14-tetradecane, trimethylol ethane,
trimethylol propane, 3-ethoxy-1,2,4,5-tetrahydroxypentane,
pentaerythritol, starches, cellulose, sugars and
alkoxylated drivatives thereof.
The dialkenyloxy carbonate coreactants (II) are
preferably those wherein R' is hydrogen or methyl, m is 1
and B is butylene, dimethylene cyclohexane or ethoxylated
or propoxylated derivatives thereof.
2 ~
W091/13~2 PCT/US91/0~_
-- 4 -- .
Examples of suita~le coreactants include bis(ethenyloxy
butyl) carbonate, bis(ethenyloxy dimethylcyclohexyl)
carbonate, bis(prop-l-enyloxy butyl) carbonate, and the
polyethoxylated or polypropoxylated derivatives thereof,
such as for example the polyethoxylated derivative of
bis(ethenyloxy butyl) carbonate, having the formula
[CH2=CHOC4H8(0CH2CH2) 3 -oco-
wherein p has a value of from l to l0.
Also provided is a pclymerizahle compound having
the formula (D)
r 0l
l R'HC=CHO(B)m-OCO-~ -R-(A)a I.
2-a
which is the reaction product of a hydroxylated reactant
(I) having the formula A-ROH and a dialkenyloxy carbonate
coreactant (II) having the formula:
O
R'HC=CHO(B)mOeO(B)mOCH=CHR' II.
wherein R is a polymeric radical selected from the group of
polyester, polyacetal, polyurethane, polyether,
polybutadiene and polycarbonate, said polymers containing
from about l0 to 50 repeating monomer units;
A is hydrogen, lower alkyl or hydroxy;
R' is hydrogen or lower alkyl;
`'
2~3~7
W091/13052 PCT/US91/~639
_ 5
B is a linear, branched or cyclic divalent radical
having from 2 to 12 carbon atoms and is selected from the
group of alkylene, mono or poly alkoxylated alkylene,
alkenylene, alkynylene, arylene, alkarylene and aralkylene
radicals, which radicals are optionally substituted with
halo, lower alkyl, cyano, nitro or alkoxy (m) has a value
of from l to l0; ~a) is zero when A is hydroxy and (a~ is
one when A is hydrogen or lower alkyl.
Reactant (I), AROH, includes hydroxylated
compounds having the formulae:
O o
HO[(R'''OC-R"-~O)nOR''']OH, a p~lye~ter;
O O
HO[(R'''-OChHR"NHCO)nOR' "]OH, a polyurethane;
X X
H(OCH2CH)nOH, alkyl(OCH2CH)nOH and HO[(CH2)40 ~H, polyethers;
H[(OR"OC)nOR"]OH, a polycarbonate;
H[OR'''OClHOR"OCH)nOR''']OH, a polyacetal, etc.
CH3 CH3
WO91/13052 2 ~ 7 5 3 ~ 7 PCT/USg1/o~
- 6 -
In the above formulae, X is hydrogen or methyl; R"
i5 C2 to C20 alkylene or arylene; R''' is C2 to C20
alkylene and n has a value of from about l0 to 50. Of
these hydroxylated polymers, the polyethers, polyesters,
polycarbonates and polyurethanes are preferred.
An aryloxy polyvinyl ether also is provided having
the formula (E)
CH20ROC8=CE~2 CH2=CHORO-CR2
CHCH2- L--~OC~i2CHCH2~ ~}A~OC}I2CH
wherein R is a linear, branched or:cyclic radical having
from 2 to 20 carbon atoms and is selec~ed from the group of
alkylene, alkyleneoxy alkylene, polya,kylene~xy alkylene,
arylene, alkarylene, alkarylalkylene and aralkylene; X is
oxygen or sulfur; A is branched or linear alkylene having
from l to 20 carbon atoms; B is halo or lower alkyl; n has
a value of from l to 20 and p has a value of from 0 to 4.
The invention also relates to the preparation and use of
said aryloxy divinyl ethers.
Preferred compounds are those wherein X is oxygen;
A is >C(CH3)2; p is zero; n has a value ~f fro~ l to 4
and R is a radical having from 2 to 8 carbon atoms.
The above carbonates (A) are synthesized by
reacting a hydroxylated al~-l-enyl ether with a dialkyl
carbonate according to the following equation.
O O
x HO(B)nOCH=CHR + R'OCOR' `A-OCO(B)nOCH=CHR + x R'OH
REACTANT I REACTANT II PRODUCT III
.
.: '
~3~S7
WO91/1~2 PCT/US91/00639
- 7 -
wherein x is l or 2; each R' is represented by lower alkyl
and R, A, B and n are ac defined above. The reaction is
carried out under mild conditions such as a temperature of
between about 65C. and about 150C. under a pressure
ranging from about atmospheric to about 50 psig. for a
period of from about l to about 30 hours, preferably at a
temperature of between about 75 and about 125C. under
ambient pressure for a period of from about l.5 to about lO
hours. This reaction is effected in an oxygen-free
atmosphere under a blanket of inert gas, e.g. nitrogen.
The reaction is promoted with between about O.Ol and about
5 wt. %, preferably between about 0.3 and about 2 wt. % of
a base catalyst including such catalysts as sodium or
potassium alkoxides, particularly methoxides; sodium or
potassium metal; sodium or potas~ium hydrQxide, hydride or
phenoxide, alkaline earth metal hydr~xides or alkoxides and
alkaline or alkali earth salts of reactant I.
Generally, the ratio of reactant I to II can vary
within the range of between about l:5 and about 15:l,
preferably between about l.2:l and about 5:l. Although the
reaction does not require the use of a diluent, an inert
liquid at a concentration of up to 50 wt. % of the reaction
mixture can be employed. Suitable diluents include
toluene, xylene, ben~ene, alkyl ethers, N-methyl-
pyrrolidone, butyrolactone, ethyl acetate and the like
which are normally liquid and have a boiling point below
that of the reaction product.
It is found that the product composition can be
varied depending uyon the initial ratio of reactant I with
respect to reactant II. Specifica]ly an excess of reactant
II produces a moncsubstituted carbonate wherein A is lower
alkyl; whereas an excess of reactant I produces a
disubstituted product wherein A is RCH=CHO(B)n-.
W091/13052 ~ PCT/US91/00~
Alternatively, the compounds of this invention where A is
lower alkyl can be prepared by reacting a Cl to C6
alcohol with a divinyloxy carbonate according to the
equation:
~1 O
R'OH + RHC=C~O(B)n~OCO~(B)nOCH=CHR -)RHC=CHO(B)n-OCO-R'
The present polycarbonates (B) are synthesized by
reacting a hydroxyalkyl alk-l-enyl ether, a diol and a
dialkyl carbonate according to the following equation.
o o o
HOROCH~CHR' l HOR"OH + R~OR"I_~.A-OClJtR'-t~ mOCO]nROCH~CHR' ~ R~H
REACSANS I REACl'ANT ~I REACTANT III PROD~lCr
wherein each R " ' is represented by lower alkyl and R, R',
R", A, m and n are as defined above.
Generally, the mole ratio of reactant I to II to
reactant III can vary within the range of between about
l:l0:20 and about l:0.5:2, preferably between about 4:l:4
and about 2:l:2. Although the reaction does not require
the use of a diluent, an inert liquid at a concentration o~
up to 50 wt. % of the reaction mixture can be employed.
Suitable diluents include toluene, xylene, benzene, alkyl
ethers, N-methylpyrrolidone, butyrolactone, ethyl acetate
and the like which are normally liquid and have a boiling
point below that of the reaction product.
It is found that the product composition can be
varied depending upon the initial ratio of reactants I, II
and III. Specifically an excess of reactant III produces
polycarbonates wherein A is lower alkyl; whereas an excess
:....................................... ~, ..... .
.
WO91/1~52 2~ 7 3 ~ 7 PCT/US91/~639
of reactant I produces a disubstituted product wherein A is
R'CH=CHOR-. Also, n in the alkenyloxy polycarbonate
product largely depends on the mole ratio of reactant III
with respect to reactant II. Thus, where a high proportion
of III is employed, the value of n is increased.
Conversely, where a low proportion of III is employed, the
value of n is low.
Alternatively, the dialkenyloxy dicarbonate
products can be prepared by reacting the diol (HOR"OH) with
a dialkenyloxy monocarbonate (A) above. The reaction
conditions for this alternative reaction are substantially
the same as those described above except that the mole
ratio of diol to carbonate reactan~:is..about 1:2. This
reaction can be defined by the ~equati~
HOR"OH + R'HC=CHOROCOROCH=CHR'
O O
R'HC=CHOROCOR"OCOROCH=CHR'
The reaction for synthesizing the above compounds
(C) is conducted in the presence of between about 0.0l and
about 5 wt. %, preferably between about 0.l and about l wt.
% of a basic catalyst such as particulate sodium, potassium
or lithium metal, sodium, potassium or lithium hydroxide,
hydride or alkoxide, e.g. methoxide, and the like. The
reactants may be diluted with up to 80% of a suitable inert
solvent such as xylene, toluene, tetrahydrofuran,
N-methylpyrrolidone, dimethylformamide, etc. Although
dilution is usually recommended for more viscous reaction
mixtures, it is also within the scope of this invention to
carry out the react1on in.the absence of solvent.
WO9l/13052 2 ~ 7 ~ ~ ~ 7 PCT/US91/~6~
-- 10 --
The reaction conditions include a temperature of
from about 50 to about 200c., a pressure of from about
1 mm Hg to about 100 atmospheres for a period of from about
0.5 to about 24 hours. Within the above operating
parameters, between about 90 and about 120C. under from
about 1 to about 10 mm Hg for a period of from about 3 to
about 7 hours are preferred. High conversions in excess of
80% are achieved by the present reaction.
The ratio of polyhydroxylated reactant to
dialkenyloxy alkyl carbonate is as close to stoichiometry
of the product desired as is convenient to maintain.
Desirably, the amount of dialkenyloxy alkyl carbonate
varies from about 1 to about 2 moles of carbonate per
equivalent of hydroxyl groups. However, it is to be
understood that excess amounts of the alkenyloxy alkyl
carbonate, up to about a 10 mole excess, can be employed
without detriment to the reaction; the only objection being
that such high excesses of the carbonate reactant are
wasteful and inefficient.
The crude product of the above reaction generally
contains a mixture of products. Thus for example when ROH
is HOCH2-CH(OH)CH(OH)CH2OH the crude product contains
one or more of the following derivatives, depending upon
the amount of coreactant employed.
R'HC=CHO(B)mOCO-R(OH)3
[ R'HC--CHO~B)mOgO3 ~ R(OH)2
... , . ~.;;
;,.
.
,
20753~7
WO91/13052 PCT/US91/00639
-- 11 --
R'HC=CHO(B)mOCO ~ ~
. ~ O-- ..
R'HC=CHO(B)mOCO- 4 _~_
The products can be separated by any conventional
means, e.g. fractional distillation, if desired.
The synthesis of the present carbonate products
(D) is expressed as follows:
AROH + R'HC=CHO(B)mOCO(B)mOCH=CHR'
[R'HC-CHO(B)m-OC0]2_aR(A)a + R'HC=CHO(B)mOH
The dialkenyloxy alkyl carbonate coreactants (II)
are the (A) compounds described above and are preferably
those wherein R' is hydrogen or methyl, m is l and B is
butylene, dimethylene cyclohexane or ethoxylated or
propoxylated derivatives thereof.
Examples of suitable coreactants include
bis(ethenyloxy butyl) carbonate, bis(ethenyloxy
dimethylcyclohexyl) carbonate, bis(prop-l-enyloxy butyl)
carbonate, bis(l-propenyloxy phenyl) carbonate,
bis(ethenyloxy benzyl) carbonate, bis(ethenyloxy xylyl)
carbonate and the polyethoxylated or polypropoxylated
derivatives thereof, such as for example the
polyethoxylated derivative of bis(ethenyloxy butyl)
carbonate, having the formula
i
WO91J1~2 2 ~ 7 ~ 3 ~ 7 PCT/US91tO06
[cH2=cHOc4H8(ocH2cH2)p~ OCO
wherein p has a value of from 1 to 10.
The above divinyl ethers (E) are synthesized by
reacting a hydroxyvinyl ether with a diepoxide of a
bisphenol such as bisphenol A epoxy resin, or a bisphenol F
epoxy resin. The reaction is effected according to the
following equation.
C82~CHOROH + CH2--CHCH~{ ~ } ~ 2~Ca2~ ~ } ~ C82CE~
~B) p ~B) p (3) p (8) p
CH20ROCEI--CH2 CH2=cHoRo-cH2
C~2Ca2~~ca2caca2~ ~oca2c~
' ,.
.~: :
, . ! , . . . .
. ' ' . , ' ' ~ , ,
,. ' ' . ~ ~ .' ' ` ,
. ,' ;' ' . ' ' . ' ' ' '
2 3 ~ ~ 3 ~ ~
WO9l/13~2 PCT/US91/00639
- 13 -
The synthesis reaction can be carried out in the
presence of air or in the absence of oxygen under a blanket
of inert gas. Generally, the present condensation reaction
is carried out at a temperature of between about 100 and
about 175C. under atmospheric pressure for a period of
from 0.5 to 200 hours. Preferred reaction parameters
include a temperature of from about 120 to about 160C.
for a period of from about 2 to about lO0 hours.
The reaction is also conducted in the presence of
a base catalyst such as particulate sodium, potassium, or
lithium ~etal, sodium or potassium hydroxide or hydride.
The catalyst is present in an amount of from about 0.01 to
about 2 wt. ~, preferably f~om abQut:0 1 to about 1 wt. %
of the total mixture. When;th~ ~eactants and products
included herein are liquids,- t~y-are generally synthesized
in the absence of diluents or solvents which are otherwise
required for more viscous or solid reactant~. Suitable
solvents include toluene, xylene, triethylene glycol
dimethyl ether, N-methylpyrrolidone and the like. Such
solvents can be employed in concentrations up to about S0%
of the reaction mixture.
The hydroxy vinyl ether reactant and the phenylic
coreactant of the present process are generally employed in
a mole ratio of from about 1:1 to about 10:1, preferably
from about 1.05:1 to about 3:1.
Suitable hydroxylated vinyl ether reactants
include the mono vinyl ether of cyclohexanedimethanol,
tetra(hydroxyethyl) vinyloxy hexane, (2-hydroxyethyl) vinyl
ether, (3-hydroxypropyl) vinyl ether, the monovinyl ether
of 3-ethyl-1,6-hexanediol, (4-hydroxybutyl) vinyl ether,
6-hydroxyhexyl vinyl ether, the monovinyl ether of
2-methyl-1,8-octanediol, (vinyloxy) cresol, vinyloxymethyl
cyclohexyl methanol and alkoxylated derivatives thereof
containing from l to 6 ethyleneoxy or propyleneoxy units.
:
.
2~7~3~7
WO91/13052 PCT/US~1/006~,
- 14 -
Suitable coreactants include
1,3-{bis4-{2-[4-(2,3-epoxypropoxy)phenyl]prop-2-yl~phenoxy}-
2-propanol,
1,3-bis{4-[4-(2,3-epoxypropoxy)benzyl]phenoxy}-2-propanol
poly(phenylalkylphenoxy-2-propanol-3-oxy)epoxypropoxy
epoxypropoxyphenylalkylphenyl and the like.
The initiators suitable to effect polymerization
reactions of the present invention can also comprise a
mixture including the above-~amed-.cat~onic initiators and a
free radical initiator to pro~ide a hybrid initiated
system. Suitable free radical initiators~include
l~hydrocyclohexyl phenyl ketone (HPK),
2-hydroxy-2-methyl-1-phenyl-1-propan-1-one (HMPP0),
2,2-dichloro-1-(4-phenoxyphenyl) ethanone (DPPE) and the
like. When initiator mixtures are employed, the free
radical component can comprise up to 75%, preferably
between about 30 and about 70%, of the initiator
component. The present cationic initiator or cationic/free
radical initiator mixtures provide the benefits of this
invention when used for cross-linking blends of the present
vinyl ether carbonate and vinyl ether or epoxide monomers.
However, when the blend contains an acrylate polymerizable
comonomer the initiator mixture is recommended. The total
amount of initiator employed is generally between about 0.1
and about 5 wt. % with respect to reactant or reactants.
Usually, exposure for less than one second is
suffic~ent to provide a completely cross-linked homopolymer
or copolymer. W light radiation dosages at room
temperature of from about 100 to about 1500 milli J/cm2
are effective and dosages of from about 200 to about 600
milli J/cm2 are preferred. Equivalent dosages for curing
are employed when using alternative sources of radiation.
... .
. ~
2~753~7
WO91/13052 PCT/US91/00639
- 15 -
For example, curing with electron beam radiation can be
carried out at be'ween about 0.5 and about 20 Mrads,
preferably between about 1 and about 10 Mrads. Specific
techniques for radiation curing are well known, thus
further amplification is not required.
As inferred above, the present products can be
mixed with a vinyl ether, epoxide, acrylate or vinyloxy
alkyl urethane monomer or polymer, or other monomers and
oligomers which otherwise would not be amenable to cationic
radiation curing, to incorporate and combine the advantages
of instant compounds with the beneficial properties of
those coating materials or other monomers and oligomers.
Examples of monomers or pol~mer~-with-.which the present
products can be combined to fo~m-cc~tings include the
1,4-butanediol diglycidyl ether; ~,4-apoxycyclohexyl
methyl-3~4-epoxy cyclohexane carboxylate; diglycidyl ethers
of bisphenol A or bisphenol F; polyglycidyl ethers of
phenol-formaldehyde, e.g. epoxy novolac resins and other
functional monomers and polymers which possess properties
beneficial in durabie protective coatings. When such
comonomeric coatings are employed, the mixture contains at
least 5% of the present alkenyl ether carbonate.
The homopolymerized and copolymerized products of
this invention have high resistance to solvents, acids and
bases and form hard abrasion resistant films and coatings,
possessing good substrate substantivity. The individual
products of this invention, as monomers or oligomers or as
mixtures thereof are also useful as chemical intermediates
and as materials which, upon hydrolysis, are capable of
forming hydrogels. Also, because cf their high radiation
sensitivity, the present compounds are suitable as
photoresist materials.
2v7.j3~ ~
WO91/13052 PCT/US91/00~.
- 16 -
PREPARATION OF COMPOUNDS (A)
EXAMPLE 1
A. A 250 ml three-necked round bottom glass flask,
equipped with a thermometer, magnetic stirrer, distillation
head, water condenser, receiver and a nitrogen inlet was
charged with 116 g. (l mole) of hydroxybutyl vinyl ether,
45 g. (0.5 mole) of dimethyl carbonate and 0.5 g. of sodium
methoxide. The mixture was heated under a blanket of
nitrogen to 82C. for 2.5 hours. An azeotrope of methanol
by-product, dimethyl carbonate and hydroxybutyl vinyl ether
was distilled off at a head temperature of about 32C. The
reaction mix.ure was then cooled and filtered. The
separated flltrate (130 g.) was f-las~ distilled at 65-85C.
under 3 mm Hg. The resulting distillate was subjected to
gas chromatography analysis which indicated 70% unreacted
hydroxybutyl vinyl ether and 30~ product. Fractional
distillation under 3 mm Hg resulted in a fraction separated
at 150-160C. (34 g.) which was analyzed as 82.4%
bis~(ethenyloxy)butyl] carbonate and 15.7%
mono[(ethenyloxy)butyl] methyl carbonate. Four grams of
methanol and dimethyl carbonate were collected in the trap.
'. .- .
' ' ' , :
WO9l~13052 2a7~3~7 PCT/US91/~639
- 17 -
B. The product fraction separated at 150-160C. was
then evaluated for a radiation cured coating according to
the following procedure. The product mixed with 2 wt. % of
triphenyl sulfonium hexafluorophosphate was coated in about
0.15 mil thickness on an aluminum panel and then subjected
to less than 1 second exposure at room temperature to 400
milli J/cm2 radiation from 2 medium pressure mercury
vapor lamps. The cured coating had strong adhesion to the
substrate and had excellent resistance to chemical attack
from acids and bases.
EXAMP_LE 2
The procedure describe~ in Example 1 was repeated
except that the reaction was carried out with an excess of
dimethyl carbonate 100 g. (1.11 mole) of dimethyl carbonate
together with 116 g. (1 mole) of hydroxybutyl vinyl ether
and 0.5 g. sodium methoxide was charged into the reactor
and progressively heated from 85C. to 110C. The reaction
mixture was distilled over a 26 hour period at a head
temperature of from 40 to 63C. to remove 38.4 g. of
methanol/dimethyl carbonate azeotrope. The filtered
product t117 g.) was then distilled in an Oldershaw 5 plate
column and the fraction separated (38.3 g.) at pot
temperature of 112-125C. and head temperature of 59C.
under 1.5 mm Hg was analyzed and found to be 99% pure
methyl [(ethenyloxy)butyl] carbonate, whose structure was
confirmed by IR and lH and 13C NMR spectral data and
elemental analysis.
2 ! 7 r ~ ~ 7
WO91/l30s2 PCT/US91/00~_,
- 18 -
EXAMPLE 3
In the apparatus described in Example 1 was
char~ed 250 g. ~2.15 mole) of hydroxybutyl vinyl ether,
~30 g. (1 mole) of dimethylcarbonate and 1 g. of sodium
~ethylate. The reaction mixture, under a blanket of
nitrogen was heated for 18 hours at a head temperature of
about 45C. to remove 39 g. of azeotropic distillate from
the reaction pot containing 48% hydroxybutyl vinyl ether,
46% bis[(ethenyloxy)butyl] carbonate and 4%
mono[(ethenyloxy)butyl] methyl carbonate. The pot
temperature was gradually raised from 85C. to 148C. over
a period of 18 hours and the product-mixture filtered to
remove undissolved catalyst and 240 g. of filtrate,
containing
CH2 CHO(cH2)4oco(cH2)4ocH=cH2
product was collected.
EXAMPLE 4
Example 3 was repeated using a 2 liter glass
flask, except that 1000 g. (8.6 moles) of hydroxybutyl
vinyl ether, 360 g. (4 moles) of dimethylcarbonate and 4 g.
of NaOCH3 were charged and heated under a blanket of
nitrogen. In this example 243 g. of the azeotrope were
removed at a head temperature of 28-65C. Also, the pot
temperature was gradually increased over a 27 hour period.
The reaction product was filtered and the
resulting product mixture was found to contain 34%
hydroxybutyl vinyl ether, 5.5% mono[(ethenyloxy)butyl]
methyl carbonate and 58% bis[(ethenyloxy)butyl] carbonate.
.
.
~7~357
WO91/130s2 PCT/US9t/00639
-- 19 --
This product
CH2=CH(CH2)4C(CH2)4CH=CH2
tlO70 g.) was then combined with 240 g. of the product
obtained in Example 3 and 1295 g. of the combined product
mixture was fractionally distilled in a 15 plate column
Oldershaw distillation apparatus at a pot temperature of
110 to 180C. and a head temperature of 70-76C. under
5-7 mm Hg to recover 385 g. of hydroxybutyl vinyl ether of
99% purity. Upon further heating, the fraction collected
at the pot temperature of 185-~lQC and head temperature
of 143-145C. under 1 mm Hg (T67 ~. ) was found to be 99.7%
pure bis[(ethenyloxy)butyl]-c3r~cn~e. During the
distillation unreacted hydroxybutyl vinyl e~her reacted
with the mono[(ethenyloxy)butyl] methyl carbonate product
to increase the bis[(ethenyloxy)butyl] carbonate content
from 730 g. to 767 g. of 99% purity. The product was
established with IR, 1H and 13C NMR spectra and
elemental analysis.
EXAMPLE 5
Example 4 was repeated except that a charge of
900 g. of hydroxybutyl vinyl ether, 472 g. of
diethylcarbonate and 4.1 g. of NaOCH3 was s~bstituted.
Also, the resulting mixture was heated at a pot temperature
gradually increasing from 115 to 155C. over 28.5 hours.
The head temperature varied from 42C. to 100C. The
corresponding ethanol/diethylcarbonate azeotrope (318 g.)
~as removed. The remaining product mixture was found to be
20% hydroxybutyl vinyl ether, 14.8% mono[(ethenyloxy)butyl]
ethyl carbonate and 63.5% bis[(ethenyloxy)butyl] carbonate.
WO91/13052 2 ~ 7 ~j 3 i~ 7 PCT/US91/00~.~
- 20 -
After filtering this product mixture and distilling as
described in Example 4, the major fraction (572 g.) boiling
off at 143-144C. under 1 mm Hg (pot temperature of
185-200C.) was found to be 99.2% pure
bis[(ethenyloxy)butyl~ carbonate. A minor fraction (218 g.)
boiling off at 160C. under 2.5 mm Hg (Pot temperature of
190C.) contained 97% bis[(ethenyloxy)butyl] carbonate and
about 3% hydroxybutyl vinyl ether. A lighter fraction
(75 g.) taken off at 66C. under 4-5 mm Hg (pot temperature
of 130-190C. ) was found to be 95% pure hydroxybutyl vinyl
ether.
EXAMPLE 6
The product from Exam~l-e 4 was mixed with an equal
weight amount of a diglycidyl et~er of hisphenol A, 1 part
2er hundred parts of resin of a fluorochemical surfactant,
and 4 parts per hundred parts of resin of a cationic
photoinitiator at 50C. until a homogeneous low viscosity
liquid was obtained. This mixture was then coated on an
aluminum substrate at a thickness of 1.2 mil. The coated
surface was exposed for less than 1 second to 400
millijoules/cm2 from a mercury vapor lamp. A tack free,
film was produced. Coating properties reported in the
following table were determined immediately after W
exposure and after a post cure at 177C. for 15 minutes.
TABLE
After W After
Property xposure Post Cure
Pencil Hardness (ASTM D 3363) 2B 2H
% Adhesion (ASTM D 3359)0 100
Double MEX Rubs 49 >100
Reverse Impact - 30
Mandrel Bend ~in.) (AS~M D 3111) 1/8 1/8
;
wo gl/l3052 ~ 3 S 7 PCT/US91/00639
- 21 -
EXAMPLE 7
The mixture described in Example 6 was coated on a
polyester substrate at a thickness of 0.5 mil. The coated
c;urface was exposed to 400 millijoules/cm2 W light for
less than 1 second and post cured for 2 hours at 50C.
Chemical resistance was tested by the covered spot test
~ASTM D 1308). ~o attack was observed after 24 hours
exposure to 1% H2SO4, 1% NaOH, 10% acetic acid, or
distilled water.
EXAMPLE 8
The product from Ex~pl~ 4 (2.5.0 gm) was mixed
with the divinyl ether of triethylen~.glycol (25.0 gm) a
bisphenol A epoxy acrylate oligomer, 2 ~hr* cationic
photoinitiator, 2 phr* free radical photo-in;tiator and 1
phr* fluorochemical surfactant at 50C. until a homogeneous
low viscosity liquid was obtained. this mixture was then
coated on a polyester substrate at a thickness of 0.5 mil.
The coated surface was exposed to 400 millijoules/cm2
from a mercury vapor lamp for less than 1 second. A tack
free coating with the following properties was produced.
Pencil Hardness 3H
Adhesion 100%
Double MEK Rubs >100
*parts/100 parts resin
WO9l/l30s2 2 0 7 ,3 3 ~3 7 PCT/USg~ J
- 22 -
EXAMPLE g
The product from Example 4 (12.5 gm) was mixed
with the divinyl ether of triethylene glycol (12.5 gm) and
a divinyl ether urethane oligomer (25.0 gm); 4 phr cationic
photoinitiator, and 1 phr fluorochemical surfactant at
50C. until a homogeneous low viscosity liquid was
obtained. This mixture was then coated on a aluminum panel
(0.50 mil) and exposed to 400 millijoules/cm2 from a
mercury vapor lamp for less than 1 second. A tack free
coating with the following properties was produced
Pencil Hardness 3B
Mandrel Bend 3~8 inch
Double MEK Rubs 18
PREPARATION OF COMPOUNDS (B)
EXAMPLE 1
A 500 ml, round bottom flask was charged with 30 g
of triethylene glycol (0.2 mole), 105 g bis(ethenyloxy-
butyl) carbonate (0.41 mole) and 0.1 g sodium methoxide.
The flask was heated under vacuum of 3 mm Hg at 100-105C.
in a Kugelrohr apparatus for a period of 4.5 hours, after
which a total of 44.3 g of distillate was collected. The
distillate was analyzed by gas chromatography (GC), and
identified as a mixture of 95% hydroxybutyl vinyl ether,
3.8% bis(ethenyloxybutyl) carbonate and 0.8~ triethylene
glycol.
The residue containing carbonate product weighed
90 g. To the residue was added 2 g Nuchar charcoal and the
mixture was heated to 60C. under vacuum for 30 minutes and
filtered.
2,~3;~7
WO91/1~52 PCT/US91/00639
- 23 -
The filtrate was a colorless liquid, weighing
83.0 g (yield of about 90%). lH NMR and IR data
identified the product as having the structure
O O
CH2=cHoc4H8oco (CH2CH2o) 3COC4H80CH CH2
The IR spectrum showed absence of OH frequency. About 98%
conversion was achieved.
EXAMPLE 2
Example l was repe~t~d e~r~pt that 21 g of
diethylene glycol (0.2 mb~é) was used-in-the place of 30 g
triethylene glycol.
The flask contents-~ere heated under vacuum, 3-5
~m Hg at 100C. for a period of 4.5 hours and 43.1 g
distillate containing a mixture of hydroxybutyl vinyl ether
and the carbonate reactant was removed.
The contents of the flask was worked up as
described in Example l. The filtrate was a clear colorless
liquid weighing 83.3 g indicating about 90% yield.
IR spectrum analysis of the product showed total
absence of OH signals. lH NMR and IR data identifed the
product as having the structure
O O
CH2=cHoc4H8oco(cH2cH2o) 2COC4H80CH CH2
More than 99% conversion was obtained.
WO91/13052 2 a I 3 3 ~ ~ PCT/US91/~639
- 24 -
EXAMPLE 3
A 500 ml round bottom flask was charged with 36 g
butenediol (0.41 mole), 220 g bis(ethenyloxybutyl)
carbonate (0.85 mole) and 0.4 g sodium methoxide. The
procedure described in Example l was repeated except that
the flask was heated at 100C. under vacuum of 6 mm Hg for
2 hours.
During this period, 166.5 g of distillate was
collected. The reaction mixture was heated at 130C. under
O.5 mm Hg vacuum, until distillation ceased and an
additional 12.5 g of distillate was collected.
The pot content was worke~ u~ as described in
Example 1 except that only 1 g of char~oal was used. A
colorless viscous liquid (67 g) which solidified on
standing was obtained. The product was identified by lH
NMR and IR spectral data as having the structure
O O
Il 11
CH2=CHGC4H80CoCH2CH=CHcH2ococ4H8ocH=cH2
EXAMPLE 4
A 500 ml round bottom flask was charged with
28.8 g cyclohexane dimethanol (0.2 mole), llO g
bis(ethenyloxybutyl) carbonate (0.43 mole) and NaOCH3
0.2 g. The procedure desc~ibed in Example l was repeated
except that the reaction mixture was heated at 100C. for
only 2.5 hours. Recovery of distillate (65.9 g) was found
to contain a m~xture Gf reactants, (~bout 20.0 g of
bis(ethenyloxybutyl) carbonate) and 43.5 g of
bis(hydroxybutyl vinyl ether).
~ ~ 7 ~ t~, ~
WO91/130s2 PCT~VS91/00639
- 25 -
The residue was worked up as in Example 1 with 1 g
charcoal (Nuchar) heated to 90C. for 30 minutes and
filtered. The filtrate was a clear colorless viscous
liquid weighing 62 g. IR and lH NMR spectral data
identified the product as having the structure
O O
CH2=cHoc4H8ococH2-c6Hlo-cH2ococ4H8ocH CH2
IR spectrum showed total absence of OH frequency.
Greater than 98% conversion was achieved.
EX~MPIE 5
The product from Example 4 (46.7 g) ~as charged
into a 100 ml round bottom flask and heated to 130C. under
a vacuum of 3 mm Hg for 1 hour. Distillate welghing 5 g,
primarily bis(ethenyloxybutyl carbonate) was removed.
Spectral analysis of the pot content showed oligomerization
of Example 5 product, i.e.
O O
CH2=cHoc4H8oco ( CH2 -C6Hlo~CH20CO) 2 _3C4H80CH CH2
EXAMPLE 6
The procedure described in Example 1 was repeated
except that the reaction mixture charged to the flask was
11 g of bisphenol A, 32.5 g bis(ethenyloxybutyl carbonate)
and 1 g of KOH. The mixture was heated at 130C. under 5
mm Hg for a period of 7 hours. The distillate was removed
and lH NMR identified the pot content as a mixture of the
following products
WO91/130s2 2 ~ 7 .~ 3 ~ ~ PCT/US91/0063Y
- 26 -
CH3 o-l-o(CH2)4cH=cH2]2 and
CO(CH2)40-~H-0 ~ ~ OCo(cH2)4ocH=cH2
CH3 CH3 CH3
EXAMPLE 7
The procedure des~ribed in Example 1 was repeated
except that the reaction mixture-c~arg~d:to the flask was
18.6 g. l-dodecanol and 25.8 g bisethenyloYy~utyl carbonate
and O.l g sodium methoxide. The flask was heated at 90C.
under vacuum of S mm Hg for 5 hours.
During this period 13 g distillate containing a
mixture of hydroxybutylvinyl ether and the carbonate
reactant was removed.
The contents of the flask was worked up as in
Example l using l g charcoal (Nuchar), heated to 60C. for
30 minutes and filtered. The filtrate was a clear
colorless liquid which solidified on cooling weighing 26 g.
IR and lH NMR spectral data identified the product as
having the structure
H2C=CH0(CH2)40C0(CH2)llCH3
~f~7.~.~'J7
WO91/13~s2 PCT/US9l/00639
- 27 -
EXAM~LE 8
Example 1 was repeated except that 62.6 g of the
bis-ethoxylate of bisphenol A was used in place of
triethylene glycol. The reaction mixture was heated under
vacuum at 3-5 mm Hg at 100C. After 2 hours 52 grams of
distillate was removed. The resulting yellowish liquid was
treated with charcoal at 50C., and filtered. The final
product was a clear viscous liquid. The 1H NMR spectrum
is consistent ~ith the following struct- ~.
CH3 O(cH2)2oco(cH2)4ocH=cH2]2
CH3
EXAMPLE 9
A four-necked 500 ml round bottom flask equipped
with a mechanical stirrer, thermometer, distillation head
and water condenser, additional funnel and nitrogen inlet
was charged with 76 g of butanediol (0.86 mole), 150 g of
dimethyl carbonate (1.7 mole), 11.6 g of hydroxybutyl vinyl
ether (0.1 mole), and 1 g of sodium methoxide. The pot
temperature was maintained at about 100C. under a blanket
of nitrogen for a period of 12 hours, during which an
azeotrope containing methanol and dimethyl carbonate was
distilled off at a head temperature of 31-35C.
The reaction mixture was filtered and flash
distilled at 120-150C. under 3 mm Hg. A solid residue (A)
weighing 85 g was recovered.
2a~ ~357
WO91/13052 PCT/US91/~Ob~9
- 28 -
The residue (A) comprised 66% of
H2C=HCo(cH2)4-[o-lcl-o(cH2)4]4ollocH3
O O
and 33% of
H2C CHO(CH2)4 [o-lcl-o(cH2)4]4o - lcl-o(cH2)4ocH=cH2
O o
which mixture was confirmed by HNMR analysis.
~'' 1,0
A 28 g portion of the r~si~u~:~A) described in
Example 10 was charqed into a 250 ml, 3 necked round bottom
flask equipped with mechanical stirrer, thermometer and a
vertical condenser attached to a vacuum line.
Hydroxybutyl vinyl ether (100 g) and sodium
methoxide (0.2 g) were added to the residue. The flask was
then heated and maintained at a temperature of 100C.,
under a vacuum of 100 mm Hg, for a period of about 6.5
hours.
The content of the flask was flash distilled at
150C. under 3 mm Hg leaving 30 g of final product (B)
which was a liquid at 30-40C. and slowly solidified at
room temperature. During the flash distillation about 90 g
hydroxybutyl vinyl ether was recovered. Product B, i.e.
H2C=CHO(CH2)4 -o--fi-o- [(CH2)4-0-1cl-0]8-9(cH2)4OcH=cH2
O O
was identified by 1HNMR analysis.
2~7~3 37
WO9l/13~2 PCT/US91/~639
- 29 -
EXAMPLE 11
A four necked, 500 ml round bottom flask equipped
with a mechanical stirrer, thermometer, distillation head
with a water condenser and a N2 inlet was charged with 70
g of butanediol (0.78 mole), 150 g of dimethyl carbonate
(1.67 mole), 11.6 g of hydroxy butyl vinyl ether (0.1 mole)
and 0.5 g of sodium methoxide. The flask was heated under
N2 by gradually raising the temperature to 105C., and
maintained at 90~C. for 1 hour followed by continued
heating up to 105C. for a total period of 12.5 hours.
During this period 90.4 g of distillate was removed at a
head t lperature of about ~C_.. No...distillate, (an
azeotrcpe of methanol and dimethylcarbonate) came off
during the distillation.
The reaction mixture was filtere~ and 141.6 g of
the filtrate was flash distilled at 120C. under a reduced
pressure of 3 mm Hg over a period of 2 hours, after which
98 g of a solid mixture was obtained. The solid product
(C)
H3Co-lC-[o(cH2)4o-lcl-]6-go(cH2)4ocH CH2
O O
and
H3COICI [(CH2)40 ICI ]6_9ocH3
O O
was identified by 'HNMR analysis.
:' -''
2 ~
WO91tl3052 PCT/US91/00
- 30 -
The solid product C (75.4 g) was charged into a
500 ml 3-necked round-bottom flask equipped with a
mechanical stirrer, thermometer-vertical water condenser
and N2 inlet. The condenser was connected to a source of
vacuum via a trap and 100 g of hydroxybutyl vinyl ether and
0.3 g of sodium methoxide were added to the flask. The
flask was heated and maintained at 100C. at a reduced
pressure of 150 mm Hg for a period of 9.5 hours. The
contents of the flask was then filtered and 162.4 g of
filtrate was flash distilled at 110C. under reduced
pressure of 3 mm Hg during which unreacted hydroxy vinyl
ether was removed, leaving 89.4 g residue which solidified
on cooling. This solid prod~ct ~as:f~nd to be
2C CHO(CH2)40~C~O[ (cH2)4olcl-o]7 - 9(cH2)4ocH=cH2
O O
EXAMP~E 12
Example 11 was repeated except that the charge to
the reactor was 50 g of residue A obtained from Example ~,
100 g of hydroxy butylvinyl ether and 0.2 g sodium
methoxide. The mixture was heated to 105C. under a vacuum
of 160 mm Hg for a period of 12 hours and the crude product
was then filtered. The filtrate, weighing 141 g, was
flash-distilled at 100C. under a reduced pressure of 3 mm
Hg for a period of 2.5 hours. The resulting product,
H2c=cHoc4H8oc~o[c4Hgo~c~o]5-6c4H8ocH CH2
O O
(5~.7 g) was recovered and solidified on cooling to room
temperature.
2~7, )57
Wogl/13052 PCTtUS91/00639
- 31 -
EXAMPLE 13
Example 9 was repeated except that the charge to
the reactor contained excess dimethyl carbonate. 90 g
butanediol (l mole), 360 g dimethyl carbonate (4 moles) and
1 g sodium methoxide. The flask was heated gradually
heated and maintained at 85-95C. for 20.5 hours during
which 165.6 g distillate, an azeotrope of methanol and
unreacted dimethyl carbonate, was collected at a head
temperature of 42-45C. Analysis of a 5 g aliquot of the
remaining liquid in the flask showed it to be a methyl
end-capped carbonate oligomer intermediate having the
structure
H3COCIiO[(cH2)4olclo]3-4c~3
Hydroxy butylvinyl ether (250 g, 2.15 mole) was
added to the flask and the temperature was raised to
135-140C. under a blanket of nitrogen for a period of 4
hours, during which 33 g of distillate was removed. The
reaction product was filtered under suction and 350 g of
the filtrate was flash-distilled at 100C. under 3 mm Hg to
remove 201 g of distillate. The oligomeric product t139 g)
having the formula
CH2=cHo(c4H8)o~c~o[(c4Hg)o~co~3-4(c4H8)ocH=cH2
O o
was recovered from the flask.
WO 91/13052 2 ~ -15 3 G ~I P~/USgl/oo~-~
-- 32 --
EXAMPLE 1 4
A four-necked 1 liter flask equipped with a
mechanical stirrer, thermometer, distillation head with a
horizontal condenser, nitrogen inlet and a receiver was
charged with 250 g of commercially available poly THF*
(polyoxybutylene diol - 250 having an average molecular
weight about 250), 360 g t4 moles) of dimethyl carbonate
(DMC) and 1 g titanium isopropoxide. The flask was heated
and maintained at 90C. for a period of 9 hours during
which 169.5 g of distillate (an azeotrope of methanol and
dimethyl carbonate) was collected at a head-temperature of
36C.
Progress of the reactiDn~was m~nitored
periodically by lHNMR data a~d:O~ ~nmher. The reaction
product was found to be a mixture- af~ methyl terminated and
OH terminated carbonate oligomers.
.
* Ho(c4H8o)3-4H
A second addition of DMC (100 g) was made to the
flask and heating continued at a pot temperature 95-97C.
under a blanket of nitrogen for 6 hours, during which
55.4 g distillate was removed. Analysis of the reaction
mixture indicated residual OH group.
A third addition of DMC (100 g) was then made and
heating continued at a pot temperature of 95-101C. for 3
hours under N2 during which an additional 118.4 g of
distillate was removed. Analysis showed the OH number of
tries reaction mixture to be 85.5 mg KOH/g. indicating
almost 80% conversion.
wo sl/13nsz ~1~ 7 ~ 7 Pcr/l ssl/~u639
A final addition of DMC (100 g) made and, heating
continued under N2 at pot temperature 105-115C., during
which 101.5 g distillate was collected at a head
temperature of 67-75C~ over a period of 6 hours. Thus, a
total of 445 g distillate was collected. The reaction
mixture, analyzed by 1HNMR data, showed practically
complete methyl terminated polycarbonate of the poly THF
diol as an intermediate product, (i.e. polyoxybutylene
diol). The OH number was found to be 20.8 mg KOH/g.
Hydroxy.~tyl vinyl ether (240 g, 2.~' moles) was
then added to the flask and heating was continued at a pot
temperature from 130 to 156C. for 6.5 hours under N2.
During this period 59 g distillat~..~ostly methanol was
removed at a head temperat~re ahout.67C. The remaining
liquid was then flash distilled at.15.0C. under a reduced
pressure of 3 mm Hg, leaving 311 g of a yellow oil in the
flask as the final product (D).
Product D was found to have the formula
Ol O
H2c=cHoc4H8oco[c4H8(oc4H8)2-3oco]2-3c4H8ocH 2
The OH number of product D 2.8 was 8.0 mg KOH/g.
EXAMPLE 15
Example 9 was repeated except that 75 g
commercially available triethylene glycol (0.5 mole), 360 g
dimethyl carbonate (4 moles), and 0.4 g sodium methoxide
were charged to the flask. The flask was heated under N2
at 85C. and 96 g of distillate was collected over a period
of 5 hours at a head temperature of 51C. The remaining
W091/13052 2 ~ 7 ~ 3 6 7 PCT/US91/00~
34 -
volatile components were removed by heating under vacuum
(140-180 mm Hg) at a temperature 50-550c. whereupon 42.5 g
additional distillate was removed at a head temperature of
42C. 1HNMR analysis of the intermediate product showed
the composition to be methyl terminated carbonate oligomer
having the formula
H3coc-o[c2H4 (C2H4) 20~1o]2CH3
Hydroxybutyl vinyl ether (120 g, 1.04 moles) was
then addecd to the flask and heating under N2 was
continued at 110C.-160C... over.. ~ ~e i~d.of 11 hours during
which period 188 g of dis~i~t~:was ~ollected at a head
temperature varying from 43 t~ 94C..until no more
distillate came off at atmospheric pressure.
The reaction mixture was then filtered and 208 g
of filtrate was flash-distilled at 170C. under 3 mm Hg
over a period of 4 hours to provide 130 g of final product
in the flask as pale yellow oil having the formula
O O
H2C=CHOC4H80CO [ C2H4 (C2H4 ) 2C] 3-4C2H40CH CH2
This product had an OH number = 19.5 mg KOH/g,
indicating greater than 97~0 conversion.
2 ~ 7 J ~ ~
WO91/1~52 PCT/US9l/00639
- 35 -
EXAMPLE 16
The product of Example 2 was mixed with an equal
amount of a diglycidyl ether of bisphenol A, 1 phr~ of a
fluorochemical surfactant and 4 phr of cationic
photoinitiator until a homogeneous low viscosity liquid was
obtained. This mixture was then coated on an aluminum
substrate in a thickness of 1.6 mil. The coated surface
was exposed for less than l second to 400 llijoules/cm2
radiation from a mercury vapor lamp. A tack-free film was
produced. Coating properties reported in the following
table were determined immediately after W exposure and
after a post cure of 177C. for. l~ minutes.
Propertv After ~VPost Cured
Pencil Hardness (ASTM D3363) 4B H
Double MEX Rubs >lO0 >100
% Adhesion (ASTM D 3359) 0 100
Reverse Impact (in-lbs) - 55
Mandrel Bend (in.) (ASTM D3111) 3/16 1/8
* parts/hundred parts of resin
EXAMPLE 17
The product of Example 3 was mixed with an equai
weight of triethylene glycol divinyl ether, 1 phr
fluorochemical surfactant and 4 phr cationic photoinitiator
until a homogeneous low viscosity liquid was obtained.
This mixture was then coated on an aluminum substrate in a
thickness of 1.4 mil. Th~ coated surface was exposed for
less than 1 second to 4~0 millijoules/cm2 radiation fror.
a mercury vapor lamp. A tack-free film was produced.
wo 91/13052 2 ~ 7 .~ 7 Pcr/usgl/0o6J~ ;
- 36 -
Coating properties reported in the fGllowing table were
determiend immediately after W exposure and after a post
cure of 177C. for 15 minutes.
Pro~rtY After W Post Cured
Pencil Hardness (ASTM D3363) <4B F
Double MEK Rubs 150 >100
% Adhesion (ASTM D 3359) 0 100
Reverse Impact (in-lbs) - 15
Mandrel Bend (in.) (ASTM D3111) 3/4 3/16
EXAMPLE 18
Example 10 was repeated e~cept that the reaction
product of Example 1 is substituted for-the reaction
product of Example 3. The following properties were
determined for the product.
ProPertv After W Post Cured
Pencil Hardness <4B <4B
Double MEK Rubs 4 lO
% Adhesion o '70
Reverse Impact (in-lbs) - 15
Mandrel Bend (in.) 7/16 5/16
EXAMPLE 19
Example 10 is repeated except that the reaction
product of Example 4 is substituted for the reaction
product of Example 3. The following properties for the
product were determined.
WO91/13~2
PCT/US91/~639
- 37 -
PropertY After W Post Cured
Pencil Hardness <4B F
Double MEK Rubs 12 80
% Adhesion o o
Reverse Impact (in-lbs) - lS
Mandrel Bend (in.) l/4 l/8
EXAMPLE 20
The product of Example 2 (50.0 gm) is mixed with
50 g of a bisphenol a epoxy acrylate oligomer, 2 phr
cationic photoinitiator, 2 phr free radical photoinitiator*
and 1 phr fluorochemical s~,Iactant at 50C. until a
homogeneous, low viscosity li~ui~ is obtained. This
mixture is then coated on a pol~e~ter.substrate at a
thickness of 0.5 mil. The coate~ s~r~ace is exposed to 400
millijoules/cm2 radiation free coating haviny a good
pencil hardness of about 3H, 100% adhesion and high
chemical resistance is obtained.
* hydroxycyclohexyl phenyl ketone
EXAMPLE 2l
The product from Example 3 (50.0 gm) is mixed with
25 g of a divinyl ether urethane oligomer, 4 phr cationic
photoinitiator and l phr fluorochemical surfactant at 50C.
until a homogeneous low viscosity liquid is obtained. This
mixture is then coated on a aluminum panel in a thickness
of 0.50 mil and exposed to 400 millijoules/cm2 radiation
from a mercury vapor lamp for less than l second. A tack
free coating havinq a good pencil hardness of about 3B, a
Mandrel bend of at least 3/8 inch is obtained.
WOgl/130s2 2 ~ 7 i~ 7 PCT/US91/~6
- 38 -
PREPARATION OF COMPOUNDS (C)
EXAMPLE 1
In a 250 ml round bottom flask 25 g. of
3,3,3-trimethylolpropane was charged along with 143 g. of
bis(ethenyloxybutyl) carbonate and 0.1 g. of sodium
methoxide. The contents of the flask was heated to
100-105C. under a vacuum of 3 mm Hg. After 6 hours, 54 g.
of hydroxybutyl vinyl ether had been distilled out of the
reaction flask. After cooling, the crude reaction product
was treated with 2 g. of charcoal at 45C. and filtered,
leaving a yellowish viscous li~ui~. The lH NMR and IR
spectrum of this material i~dicat-ed the mixture of products
shown
C~H2
80% ~CH2=CHOC4H80C0]3-cH2cl-cH2
C2H5
CH20H
15% [CH2=cHoc4H8oco]2-cH2cî-cH2
C2H5
O C~ 2H5
5% CH2=C~Oc4HgococH2-c-cH2oH
CH20H
.
S 7
WO91/1~K2 PCT/US91/00639
- 39 -
EXAMPLE 2
The product from Example l is mixed with an equal
weight of triethylene glycol divinyl ether, l phr (part per
hundred) fluorochemical surfactant and 4 phr cationic
photoinitiator. The resulting low viscosity liqu J is
coated on a polyester substrate (2.0 mil thicknes: and
exposed to 400 millijoules/cm2 from a mercury vapor
lamp. A tack free, chemically resistant coating is
produced.
EXAMPLE 3
Example l was repe~ted eYcept that 25 g. of
1,2,6-trihydroxyhexane was substi-~ut~d for
trimethylolpropane. The resulti~g pr~duct was a yellow
viscous oil. The lH NMR and IR spectra of this material
indicated a mixture of the compounds:
[CH2=CHOC4H8OCO]3-CH2-CH(CH2)4-
[CH2=CHOC4H8OCO]2-CH2-~CH(CH2)4-
OH
CH2=cHoc4H8oco-cH2-lH-(cH2)4OH
OH
and isomers thereof.
.
2~7.,3~ 7 .
WO91/130~2 PCT/US91/00
- 40 -
PREPARATION OF COMPOUNDS (D)
.
EXAMPLE 1
In a 250 ml, one necked, round bottom flask, 80 g.
(0.08 mole) polyethylene glycol with an average molecular
weight of 1000 was charged along with 56 g.
bis(ethenyloxybutyl) carbonate (0.22 mole) and 0.2 g.
sodium ethoxide. The flask was heated under vacuum at 3 mm
Hg, at 100-105C. in a Kugelrohr apparatus for a period of
7 hours after which a total of 22.5 g. distillate was
collected. The distillate was ide~tified by GC analysis as
a mixture containing 75-~0% hy~r~xybutyl vinyl ether and
20-25% of bis(ethenyloxybutyl) c~rbonate. About 90%
conversion was achieved. -
The contents of the fla~sk c~ntaining the majorproduct of the reaction was treated with ~ g. (Nuchar)
charcoal and filtered at about 45C. The filtrate
solidified on standing yielding 98 g. of a clear colorless
waxy solid which was identified as product having the
formula
O O
CH2=cHoc4H8oco(cH2cH2o)2ococ4H8ocH CH2
by lH NMR and IR spectral analysis. a conversion of
87.6% was achieved.
EXAMPLE 2
In a 100 ml, one-necked, round bottom flask, 20 g.
of Duracarb 120 (a hydroxy terminated lower alkyl
polycarbonate of molecular weight ~ 850 g/mol) and 125 g.
bis(ethenyloxybutyl) carbonate were mixed together with 0.1
g. of sodium methoxide. The contents of the flask was
2 ~7 ~J `3 ~7
WO91/13052 PCT/US91/00639
41 -
heated to 100C. while under a vacuum of 3 mm Hg. After 3
hours, 3.4 g. of hydroxybutyl vinyl ether by-product had
been distilled from the reaction mixture.
The contents o f the flask containing the product
of this invention was treated with 1 g. of (Nuchar)
charcoal and filtered at 45C. Upon standing the filtrate
solidified to give 25 g. of a white, waxy solid. Analysis
by lH NMR indicated the polycarbonate bis(ethenyoxybutyl)
end capped product.
PREPARATION OF COMPOUNDS (E)
EXAMPLE 1
Hydroxybutyl vinyl et~er (19O0 g), bisphenol A
epoxy resin (345.6 g) and potassium hy~roxide (0.5 g) were
chargwd to a three liter flask~e~uippe~ with a mechanical
stirrer, thermometer, nitrogen inlet a~ a condenser
adapted with a drying tube. The solution was heated at
120C. for 24 hours and 150C. for 48 hours, after which
400 g of the resulting solution was transferred to a one
liter flask. Unreacted hydroxybutyl vinyl ether was
stripped off and 300 ml of toluene was added. The
resulting solution was washed five times with 300 ml of
water, dried over calcium sulfate and filtèred. After
stripping off toluene solvent, the substantially pure
divinyl ether product having the structure:
CH =CHOC4~ -~2
C~2OC1H8OCH=CH2 2 8
C C~2- ~ ~ (CH3) ~ CH2CHCH2~ ~ _(C:~3 ~ OH
was obtained as a yellow viscous oil.
WO91/l3052 2 ~ 7 .i 3 i~ 7 PCT/US91/00~
- 42 -
The above product was then evaluated for a
radiation cured coating by coating in about 0.15 mil
thickness on an aluminum panel and then exposing for less
than 1 second at room temperature to 400 milli J/cm2
radiation from 2 medium pressure mercury vapor lamps. The
cured coating had strong adhesion to the substrate and had
excellent resistance to chemical attack from acids and
bases.
EXAMPLE 2
Cyclohexanedimethanol (1802.6 g) and potssium
hydroxide (85~ pellets, 36 g) werOE-c~&rged into a one
gallon stainless steel autocla~e. The autoclave was
initially purged with nitrogen at roo~-temperature and then
twice at 110C. under 20 mm Hg vacuum for 0.5 hour.
Propane (100 psig) was added, the solution was heated to
160C., after which the propane pressure was readjusted to
lO0 psig and acetylene (100 psig) was added to initiate the
vinylation. After 4 hours, the reaction was halted and 46%
(642 g) of product was then recovered in 99% purity by
twice distilling the crude mixture in a 15 plate Oldershaw
column at 103C. under 4 mm Hg.
The cyclohexanedimethanol monovinyl ether product
(469.3 g), bisphenol A epoxy resin (150 g) and potassium
hydroxide (85% pellets, 0.5 g) were charged into a flask
equipped as described in Example 1. The solution was
heated to 150C. for 48 hours and then cooled to room
temperature. The resulting crude product (300 g), 500 ml
of toluene and 2 g of magnesium silicate were then
transferred into a 1 liter flask wherein the mixture was
stirred for 1 hour at room temperature and then filtered.
2 i~ 7
WO91/13052 PCT/US91/00639
- 43 -
After toluene and unreacted cyclohexane methanol vinyl
ether were stripped off, the divinyl ether of bisphenol A
epoxy resin product having the structure
CH2OCH ~ CH ~CH=CH
1 2 2 CH2=cHocH2 ~ CH201:i2
CHCH2 - L~ 3 2~0CH2 ,C~CH~ _~ (CH3)2 ~ OCH2Ci
was obtained as a pale yellow jelly.
EX~MPr~ 3
Hydroxyethyl vinyl ether (4.3~ .g), bisphenol A
epoxy resin (282 g) and potassium hydroxi~e (0.5 g, 85%
pellets) were charged into a 1 liter flask eyuipped as
described as in Example 1. The solution was heated and
held at reflux for 56 hours, after which the solution was
cooled to room temperature, stirred with 5 g of magnesium
silicate for 1 hour and filtered. Unreacted, excess
hydroxyethyl vinyl ether was stripped off and the divinyl
ether of bisphenol A epoxy product having the structure:
1~2OC2~4OCH-CH2 CH2'C~OC2H4 O-C1~2
C~C~2~ r ~ (C~3) ~ ~2C CR23 ~ C(CH3 ~ CC~2c
was obtained as a pale yellow oil.
, ~ . , .
- ' -
2 3 7 ,; ~
WOgl/13052 PCT/US9l/OOo~Y
- 44 -
EXAMPLE 4
Hydroxybutyl vinyl ether (648 g), bisphenol epoxy
resin (498 g) and potassium hydroxide (0.5 g) were charged
into a two liter flask equipped as described in Example 1.
The solution was heated at 120C. for 24 hours and then at
158C. for 48 hours. Magnesium silicate (10 g) was added
to the solution, the resulting mixture was stripped for 1
hour at 40C. and then filtered. The unreacted excess
hydroxybutyl vinyl ether was st~ipped off and the divinyl
ether product having the structure:
1~2 C4~8ocH=cH2 2 4 3 0-C:~2
C~CH2- r ~ 2 ~ H2C~C~2~ ~ 2 ~ ~C~2l,~
was recovered as a yellow viscous oil.
