U.S. patent number RE29,131 [Application Number 05/699,471] was granted by the patent office on 1977-02-01 for radiation-curable acrylate-capped polycaprolactone compositions.
This patent grant is currently assigned to Union Carbide Corporation. Invention is credited to Oliver Wendell Smith, David John Trecker, James Edward Weigel.
United States Patent |
RE29,131 |
Smith , et al. |
February 1, 1977 |
Radiation-curable acrylate-capped polycaprolactone compositions
Abstract
Unsaturated acrylate-capped polycaprolactone polyol derivatives
are produced having terminal acrylyl groups and at least one
polycaprolactone polyol chain residue in the molecule. In one of
its simplest forms the final product can be the reaction product of
a polycaprolactone diol an organic isocyanate and hydroxyethyl
acrylate. These novel derivatives can be used to produce novel
coating compositions that are readily cured to solid protective
films.
Inventors: |
Smith; Oliver Wendell (South
Charleston, WV), Weigel; James Edward (White Plains, NY),
Trecker; David John (South Charleston, WV) |
Assignee: |
Union Carbide Corporation (New
York, NY)
|
Family
ID: |
22086919 |
Appl.
No.: |
05/699,471 |
Filed: |
June 24, 1976 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
6918 |
Jan 29, 1970 |
|
|
|
Reissue of: |
069127 |
Sep 2, 1970 |
03700643 |
Oct 24, 1972 |
|
|
Current U.S.
Class: |
528/75; 525/418;
528/80; 525/920; 525/445; 522/90; 525/455; 525/925;
525/440.072 |
Current CPC
Class: |
C08G
18/4277 (20130101); C08G 18/672 (20130101); C08G
63/08 (20130101); C08G 18/672 (20130101); C08G
18/42 (20130101); Y10S 525/92 (20130101) |
Current International
Class: |
C08G
18/42 (20060101); C08G 18/67 (20060101); C08G
63/08 (20060101); C08G 63/00 (20060101); C08G
18/00 (20060101); C08G 022/16 (); C08G 017/02 ();
C08G 041/04 () |
Field of
Search: |
;260/67,78.3R,77.5AN |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3297745 |
January 1967 |
Fekete et al. |
3509234 |
April 1970 |
Burlant et al. |
3553174 |
January 1971 |
Hausslein et al. |
3553249 |
January 1971 |
Brotherton et al. |
3554886 |
January 1971 |
Colomb et al. |
|
Foreign Patent Documents
|
|
|
|
|
|
|
619,925 |
|
0000 |
|
BE |
|
693,267 |
|
Jul 1967 |
|
BE |
|
694,782 |
|
Jul 1967 |
|
BE |
|
639,619 |
|
Apr 1962 |
|
CA |
|
1,505,416 |
|
Dec 1967 |
|
FR |
|
Primary Examiner: Cockeram; H.S.
Attorney, Agent or Firm: Fazio; Francis M.
Parent Case Text
This application is a continuation-in-part of Ser. No. 6,918, filed
Jan. 29, 1970, now abandoned.
Claims
What is claimed is:
1. Acrylate-capped polycaprolactones comprising compositions from
the group consisting of:
wherein
Z is hydrogen or methyl;
Q is the residue remaining after reaction of the caprolactone
polyol with the carboxylic, isocyanato and acrylyl compound;
G is the monovalent residue remaining after reaction of a
substituted or unsubstituted monocarboxylic acid or monoisocyanate
with the caprolactone polyol and acrylyl compound and is alkyl,
aryl, .[.alkenyl,.]. aralkyl, alkaryl or cycloalkyl having up to
about 12 carbon atoms;
G' is the polyvalent residue remaining after reaction of a
substituted or unsubstituted polycarboxylic acid or polyisocyanate
with the caprolactone polyol and acrylyl compound and can be a
linkage linear or branched alkylene having from 1 to about 10
carbon atoms, or arylene, alkarylene and aralkylene having from 6
to about 12 carbon atoms, cycloalkylene having from 5 to about 10
carbon atoms, and bicycloalkylene having from 7 to about 15 carbon
atoms;
R is a linear or branched divalent alkylene having from 2 to about
5 carbon atoms;
X is alkyl having from 1 to about 3 carbon atoms or phenyl;
x is an integer having a value of from 1 to 4;
y is an integer having a value of 1 to 3;
y' is an integer having a value of 1 to 3;
the sum of y plus y' is from 2 to 4;
w is an integer equal to the valence of G' and can be from 2 to
about 4;
n is an integer having a value of from 1 to about 10; and
z is an integer having a value of one.
2. Acrylate-capped polycaprolactone esters as claimed in claim 1
comprising compositions from the group consisting of: ##STR77##
wherein Z, Q, G, G', x, y, y' and w have the same meanings as
defined in claim 1.
3. Acrylate-capped polycaprolactone urethanes as claimed in claim
1, comprising compositions from the group consisting of: ##STR78##
wherein Z, Q, G, G', R, y, y', w and x have the same meanings as
defined in claim 1.
4. Acrylate-capped polycaprolactone as claimed in in claim 1,
comprising compositions of the formula: ##STR79##
5. Acrylate-capped polycaprolactone as claimed in claim 1,
comprising compositions in claim 1, comprising compositions of the
formula: ##STR80##
6. Acrylate-capped polycaprolactone as claimed in claim 1,
comprising compositions of the formula: ##STR81##
7. Acrylate-capped polycaprolactone as claimed in claim 1,
comprising compositions of the formula: ##STR82##
8. Acrylate-capped polycaprolactone as claimed in claim 1,
comprising compositions of the formula: ##STR83##
9. Acrylate-capped polycaprolactone as claimed in claim 1,
comprising compositions of the formula: ##STR84##
Description
BACKGROUND OF THE INVENTION
Many useful coating compositions are known in commerce. However, it
is always desirable to obtain new compositions which will rapidly
produce tough, durable, protective coatings without releasing
excessive amounts of volatile vapors to the surrounding atmosphere.
Recent accomplishments have produced so-called 100 percent solids
coating compositions which are, in essence, reactive compositions
that are essentially free of volatile solvents and contain diluent
molecules that react during the curing process to become a part of
the protective coating itself. Many such compositions are known to
those skilled in the art and the term 100 percent solids coating
composition is used to denote them. These known compositions,
however, are often too viscous or do not cure rapidly enough for
some commercial applications.
SUMMARY OF THE INVENTION
It has been found that the polycaprolactone polyols, as hereinafter
defined, that contain at least one free hydroxyl group will react
with acrylic acid or hydroxyalkyl acrylates to produce an
acrylate-capped polycaprolactone derivative. It has also been found
that an organic polyisocyanate can be reacted with an hydroxyalkyl
acrylate and a polycaprolactone polyol to produce an
acrylate-capped polycaprolactone urethane. Similarly, a
silicon-containing compound can be reacted to produce an
acrylate-capped polycaprolactone silicone derivative.
It has also been found that acrylate-capped polycaprolactone
compounds can be used per se as coating compositions or they can be
admixed with other compounds to produce coating compositions. As is
obvious, any of the known pigments, fillers, additives, etc.,
ordinarily used in the production of coating compositions can be
present. The coating compositions can be applied to a surface by
any convenional manner and cured by the usual curing processes.
DETAILED DESCRIPTION OF THE INVENTION
(1) the acrylate-capped polycaprolactone compounds
The acrylate-capped polycaprolactone compounds can be defined by
the following formulas:
______________________________________ ##STR1## IIA ##STR2## IIB
##STR3## IIC ##STR4## IID ##STR5## III ##STR6## IV ##STR7## In
Formula I to IV inclusive, Z is hydrogen or methyl; Q is the
residue remaining after reaction of the caprolactone polyol, which
is hereinafter more fully described; G is the monovalent residue
remaining after reaction of a substituted or unsubstituted
monocarboxylic acid or monoisocyanate and can be alkyl, aryl,
.[.alkenyl,.]. aralkyl, alkaryl or cycloalkyl having up to about 12
carbon atoms; G' is the polyvalent residue remaining after reaction
of a substituted or unsubstituted polycarboxylic acid or
polyisocyanate and can be nothing (when the divalent acid is oxalic
acid), linear or branched alkylene having from 1 to about 10 carbon
atoms; or arylene, alkarylene and aralkylene having from 6 to about
12 carbon atoms, cycloalkylene having from 5 to about 10 carbon
atoms, and bicycloalkylene having from 7 to about 15 carbon atoms;
R is linear or branched divalent alkylene having from 2 to about 5
carbon atoms; X is alkyl having from 1 to about 3 carbon atoms or
phenyl; x is an integer having a value of from 1 to 4; y is an
integer having a value of 1 to 3; y' is an integer having a value
of 1 to 3; the sum of y plus y' is from 2 to 4; w is an integer
equal to the valence of G' and can be from 2 to about 4; n is an
integer having a value of from 1 to about 10;
The polycaprolactone polyol residue represented by Q is produced
from caprolactone or a caprolactone polyol. The caprolactone
polyols, whether monohydric or polyhydric, are commercially known
compositions of matter and are fully described in U.S. 3,169,945.
As used in this specification the terms caprolactone polyols and
polycaprolactone polyols include compounds having one or more
hydroxyl groups. As described therein the caprolactone polyols are
produced by the catalytic polymerization of an excess of the
caprolactone compound with an organic functional initiator having
at least one reactive hydrogen atom; the polyols can be single
compounds or mixtures of compounds, either can be used in this
invention. The method for producing the caprolactone polyols is of
no consequence. The organic functional initiators can be any
hydroxyl compound, as shown in U.S. 3,169,945, and include
methanol, ethanol, propanol, decanol, benzyl alcohol, and the like;
diols such as ethylene glycol, diethylene glycol, triethylene
glycol, 1,2-propylene glycol, dipropylene glycol, 1,3-propylene
glycol, polyethylene glycol, polypropylene glycol,
poly(oxyethylene-oxypropylene) glycols and similar polyalkylene
glycols, either block, capped or heteric, containing up to about 40
or more alkyleneoxy units in the molecule,
3-methyl-1,5-pentanediol, cyclohexanediol,
4,4'-methylenebiscyclohexanol, 4,4'-isopropylidene-biscyclohexanol,
xylendiol, 2-(4-hydroxymethylphenyl)-ethanol, and the like; triols
such as glycerol, trimethylolpropane, 1,4-butanediol,
1,2,6-hexanetriol, triethanolamine, triisopropanolamine, and the
like; tetrols such as erythritrol, pentaerythritol, N,N,N',N'
-tetrakis(2 -hydroxyethyl)ethylenediamine, and the like.
When the organic functional initiator is reacted with the
caprolactone a reaction occurs that can be represented in its
simplest form by the equation: ##STR8## In this equation the
organic functional initiator is the R"--(OH).sub.x compound and the
caprolactone is the ##STR9## compound; this can be caprolactone
itself or a substituted caprolactone wherein R' is an alkyl,
alkoxy, aryl, cycloalkyl, alkaryl or aralkyl group having up to
twelve carbon atoms and wherein at least six of the R' groups are
hydrogen atoms, as shown in U.S. 3,169,945. The polycaprolactone
polyols that are used to produce the acrylate-capped
polycaprolactone polyols of this invention are shown by the formula
on the right hand side of the equation; they can have a molecular
weight of from 130 to about 20,000. The preferred caprolactone
polyol compounds are those having a molecular weight of from about
175 to about 2,000. The most preferred are the polycaprolactone
diol compounds having a molecular weight of from about 175 to about
500 and the polycaprolactone triol compounds having a molecular
weight of from about 350 to about 1,000; these are most preferred
because of their low viscosity properties. In the formula m is an
integer representing the average number of repeating units needed
to produce the compound having said molecular weights.
In the reaction of the polycaprolactone polyol with the acrylyl
compound to produce the acrylate-capped polycaprolactone compound
the reaction occurs at the hydroxyl group. Thus, when a
monofunctional organic functional initiator is used to produce the
polycaprolactone polyol, the residue thereof after reaction with
the acrylyl compound can be represented by the formula: ##STR10## A
difunctional organic functional initiator produces a
polycaprolactone polyol that has the divalent residue of the
formula ##STR11## The residue from a polycaprolactone polyol
produced with a trifunctional organic funcional initiator has the
formula: ##STR12## Finally, the residue from a polycaprolactone
polyol produced with a tetrafunctional organic functional initiator
has the formula: ##STR13## Thus, as used in this applicaion, the
term "residue remaining after reaction of the polycaprolactone," as
well as variants of this term, are defined by the Formulas V to
VIII inclusive; these formulas with the oxygen atom outside the
brackets removed represent the Q variable in Formulas I to IV
inclusive. In Formulas V to VIII the R" is the residue of the
organic functional initiator; this term having the accepted meaning
established in U.S. 3,169,945.
The monovalent residue of a monocarboxylic acid or monoisocyanate
represented by G in Formulas IIA and IIC is obtained from a
monocarboxylic acid or from a monoisocyanate, respectively. The
polyvalent residue of a polycarboxylic acid or polyisocyanate
represented by G' in Formulas IIB and IID is obtained from a
polycarboxylic acid or polyisocyanate, respectively. Suitable
carboxylic acids are those containing from one to about 20 carbon
atoms, either saturated or unsaturated. These are well known and
illustrated thereof one can mention formic acid, acetic acid,
acetic anhydride, propionic acid, butyric acid, hexanoic acid,
decanoic acid, stearic acid, arachidic acid, 3-butenoic acid,
angelic acid, hydrosorbic acid, sorbic acid, crotonic acid,
1,2-dimethylbutyric acid, benzoic acid, 2-methylbenzenecarboxylic
acid, naphthoic acid, oxalic acid, malonic acid, succinic acid,
glutaric acid, brassylic acid, maleic acid, fumaric acid,
glutonaconic acid, 2-octenedioc acid, 4-amyl-2,5-heptadienedioc
acid, 1,1,5-pentanetricarboxylic acid, tricarballylic acid,
phthalic acid, phthalic anhydride, terephthalic acid, and the like.
Suitable organic isocyanates are the known aliphatic and aromatic
isocyanates such as methyl isocyanate, ethyl isocyanate,
chloroethyl isocyanate, chloropropyl isocyanate, chlorohexyl
isocyanate, chlorobutoxypropyl isocyanate, hexyl isocyanate, phenyl
isocyanate, the o-, m-, and p- chlorophenyl isocyanates, benzyl
isocyanate, naphthyl isocyanate, o-ethylphenyl isocyanate, the
dichlorophenyl isocyanates, methyl isocyanate, butyl isocyanate,
n-propyl isocyanate, octadecyl isocyanate,
3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane,
di(2-isocyanatoethyl)-bicyclo[2.2.1]-hept-5-ene-2,3-dicarboxylate,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
4,4'-diphenylmethane diisocyanate, dianisidine diisocyanate,
tolidine diisocyanate, hexamethylene diisocyanate, the m- and
p-xylylene diisocyanates, tetramethylene diisocyanate,
dicyclohexyl-4,4'-methane diisocyanate,
cyclohexane-1,4-diisocyanate, 1,5-naphthylene diisocyanate,
4,4'-diisocyanate diphenyl ether, 2,4,6-triisocyanate toluene,
4,4',4"-triisocyanate triphenyl methane,
diphenylene-4,4-diisocyanate, the polymethylene
polyphenylisocyanates, as well as any of the other organic
isocyanates known to the average skilled chemist. Of course,
mixtures of acids or mixtures of isocyanates can be used.
As is evident, the residue of a carboxylic acid is that portion of
the molecule less the carboxyl groups, e.g. the residue of acetic
acid is CH.sub.3 --, the residue of decanoic acid is C.sub.9
H.sub.19 --, the residue of benzoic acid is phenyl, the residue of
glutaric acid is --C.sub.3 H.sub.6 --, the residue of phthalic
anhydride is phenylene, etc. It is also evident that the same
applies to the organic isocyanates; thus, the residue of
methylisocyanate is CH.sub.3 --, the residue of phenyl isocyanate
is phenyl, the residue of tolylene diisocyanate is tolylene, the
residue of hexamethylene diisocyanate is --C.sub.6 H.sub.12 --,
etc.
The group G' can be illustrated by phenylene, tolylene naphthylene,
xylylene, biphenylene, ##STR14## tetramethylene, hexamethylene,
decamethylene, cyclohexylene, ##STR15## methylcyclohexylene,
##STR16## and the like. This G' is the divalent residue of any
organic polyisocyanate, substituted or unsubstituted.
Illustrative of R one can mention the divalent radicals ethylene,
1,3-propylene, 1,2-propylene, butylene, pentylene, and the like.
Suitable alkyl groups, dependent on the chain length definition set
forth, are methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
pentyl, neopentyl, hexyl, octyl, 2-ethyloctyl, decyl, dodecyl, and
the like. These are all obvious and known to those skilled in the
art.
The acrylyl compounds suitable for use in producing the
acrylate-capped polycaprolactones are acrylic acid, methacrylic
acid, or the hydroxylalkyl acrylates and the hydroxyalkyl
methacrylates of the formula ##STR17## wherein Z and R are as
previously defined. The hydroxyalkyl acrylyl compounds are well
known and can be illustrated by hydroxypropyl acrylate,
hydroxypentyl methacrylate, hydroxylpropyl acrylate, hydroxypentyl
methacrylate, and the like.
The acrylate-capped polycaprolactone polyol derivatives can be
produced by several procedures and can be single compounds or
mixtures of compounds; several preferred embodiments will be shown.
In their production a solvent can be used and the solvent is
preferably one which does and contain active hydrogen groups, i.e.
hydroxyl, amino, amido, etc., in the solvent molecule. Among the
suitable solvents one can mention the hydrocarbons such as octane,
benzene, toluene, the xylenes, etc.; the ketones such as acetone,
methyl ethyl ketone, etc.; the ethers such as diisopropyl ether,
di-n-butyl ether, etc.; and the reactive solvents normally used in
producing coating compositions that subsequently become
incorporated in the coating such as styrene, alpha-methylstyrene,
methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethoxyethyl
acrylate, 2-butoxyethyl acrylate, 2-ethylhexyl acrylate, butyl
methacrylate, 2-phenylethyl acrylate, 2-phenoxyethyl acrylate,
furfuryl acrylate, etc.
The acrylate-capped polycaprolactone polyols of Formula I can be
produced by heating a mixture of a polycaprolactone polyol with
acrylic acid or methacrylic acid. Varying the concentration of the
acrylic acid compound and the time and temperature of the reaction
will enable one to produce a mono-acrylate in which x is one or a
poly-acrylate in which x is 2, 3 or 4. Of course x cannot be
greater than 2 if a poly-caprolactone diol is used, it cannot be
greater than 3 with a polycaprolactone triol and it can be as high
as 4 with a polycaprolactone tetrol. The reaction is preferably
carried out at the reflux temperature and an esterification
catalyst can be present. The concentration of acrylic acid compound
can vary from about one mole to about 10 moles per mole of
polycaprolactone polyol used. Since the esterification reaction
requires one carboxyl group from the acrylic acid compound per
hydroxyl group present in the poly-caprolactone polyol the
concentrations of each reactant are generally based on the
equivalent amounts needed to complete the reaction, with a minor
excess of the acrylic acid compound generally charged when one
wishes to esterify all of the hydroxyl groups present in the
starting polycaprolactone polyol. One can also control the reaction
and produce an acrylate-capped polycaprolactone polyol that has
unreacted hydroxyl groups still present. For example, by the
reaction of one mole of acrylic acid with one mole of the
polycaprolactone diol having an average molecular weight of about
530, which diol is the reaction product of diethylene glycol and
epsilon-caprolactone. This 1:1 molar ratio reaction yields the
mono-hydroxyl mono-acrylate-capped polycaprolactone that can be
represented by the general formula:
the 2:1 molar ratio reaction would produce the di-acrylate capped
polycaprolactone of the general formula:
the acrylate-capped polycaprolactone esters of Formula IIA are
produced by reaction a compound of Formula I having at least one
free hydroxyl group with a monocarboxylic acid or its anhydride
while the esters of Formula IIB are produced by reacting a compound
of Formula I having a free hydroxyl group with a dicarboxylic acid
or its anhydride. This latter reaction is carried out under known
esterification conditions, as is the reaction to produce compounds
of Formula I. Esterification catalysts can be present in small
amounts, 0.01 to 5 weight percent; for example, p-toluene sulfonic
acid, sulfuric acid, tetrabutyl titanate, etc. In carrying out the
reaction an excess of the carboxylic acid is preferably present.
The esterification reaction is preferably carried out in a solvent
which can be used to azeotrope the water away from the reaction
mixture. This technique is common. At the completion of the
reaction, the acid catalyst is neutralized by conventional means
and the reaction product is dried and recovered using conventional
drying means, e.g., sodium sulfate, molecular sieves, etc., and
conventional recovery procedures, e.g., filtering, decanting,
distillation, etc.
When a monocarboxylic acid is reacted with a monohydroxyl
mono-acrylate-capped polycaprolactone of Formula I, the product has
the formula: ##STR18## The mono-hydroxyl di-acrylate-capped
polycaprolactones of Formula I produce compounds of the following
formula when reacted with a mono-carboxylic acid: ##STR19## The
di-hydroxyl mono-acrylate-capped polycaprolactones of Formula I
react with a mono-carboxylic acid to produce compounds of the
formula: ##STR20## Similarly, the mono-hydroxyl triacrylate-capped
polycaprolactones of Formula I react with the monocarboxylic acids
to produce compounds of the formula: ##STR21## and the di-hydroxyl
di-acrylate-capped and tri-hydroxyl mono-acrylate capped
polycaprolactones produce, respectively, compounds of the formula:
##STR22## and ##STR23## Of course, one can leave some of the
hydroxyl groups unesterified. The manner of doing so is well known
in the art. Illustrative of one type of such product are compounds
of the formula: ##STR24## All of the compounds represented by the
subgeneric Formulas IIA1 to IIA7 set forth in this paragraph fall
within the scope of Formula IIA.
The acrylate-capped polycaprolactone urethanes of Formula IIC are
produced by reacting a compound of Formula I having at least one
free hydroxyl group with an organic monoisocyanate. The reaction is
carried out under anhydrous conditions in the presence of any of
the known urethane catalysts such as the amines or tin compounds.
These catalysts are so well known that they should not require more
than a brief mention. They include triethylene diamine, morpholine,
N-ethyl-morpholine, piperazine, triethanolamine, triethylamine,
N,N,N',N'-tetramethylbutane-1,3-diamine dibutyltin, dilaurate,
stannous octoate, stannous laurate, dioctyltin diacetate, lead
octoate, stannous oleate, stannous tallate, dibutyltin oxide, etc.
The reaction is preferably carried out by the slow addition of the
isocyanate to the mixture of catalyst and acrylate-capped
polycaprolactone polyol; an inert solvent can be present if
desired. The temperature of the reaction can be from about
10.degree. C. to about 90.degree. C.
The subgeneric formulas for the acrylate-capped polycaprolactone
urethanes produced with a monoisocyanate correspond to Formulas
IIA1 to IIA7 with the exception that the --OOCG group of said
formulas is replaced by an --OOCNHG group.
The urethane compounds of Formula IID are similarly produced by
reacting a compound of Formula I having a free hydroxyl group with
an organic polyisocyanate such as tolylene diisocyanate.
The acrylate-capped polycaprolactone urethanes of Formula III can
be produced by heating a mixture of polycaprolactone polyol,
hydroxyalkyl acrylate and organic isocyanate, preferably in contact
with one of the hereinbefore described catalysts for the urethane
reactions. The reaction can also be carried out by adding the
organic isocyanate to a mixture of the other components, or by
feeding the polycaprolactone polyol and hydroxyalkyl acrylate,
either as a mixture or in separate streams, to the organic
isocyanate. In any instance, the reaction can be carried out either
in the presence or absence of a solvent, as hereinbefore
described.
The mole ratio of the polycaprolactone polyol to hydroxyalkyl
acrylate can range from 1:0 to 1:25 preferably from 1:2 to 1:5 with
sufficient organic isocyanate being added to react with all or
substantially all of the hydroxyl groups present.
The reaction temperatures can vary from about 20.degree. C. to
about 90.degree. C. or higher; preferably from about 50.degree. C.
to about 75.degree. C. The reaction time will vary according to the
size of the batch, the nature of each of the organic isocyanate,
polycaprolactone polyol and acrylyl compound, as well as the
reaction temperature employed.
The reaction can be carried out in air or in an inert gas
atmosphere. Precautions should be taken to exclude water, which is
known to react with the isocyanate group. To prevent premature
reaction of the unsaturated acrylyl group, about 5 to 1,000 p.p.m.
of a compound known to inhibit free radical polymerization can be
added. These inhibitors are well known and include phenothiazine,
hydroquinone, the monomethyl ether of hydroquinone,
2,6-di-t-butyl-p-cresol and other hindered phenols.
The acrylate-capped polycaprolactone siloxanes of Formula IV can be
produced by the procedures used for producing the compounds of
Formula III. The only difference is that there is additionally
present a siloxane polymer. The preferred siloxane polymers are the
methoxy capped dimethyl silicones, the methoxy capped diphenyl
silicones and the methoxy capped methyl phenyl silicones having
from 1 to 10 silicon atoms in the molecule. The reaction is carried
out at from about 10.degree. C. to about 90.degree. C., preferably
from about 40.degree. C. to about 60.degree. C. The concentration
of siloxane polymer charged can vary from 0.1 to 3 moles per mole
of polycaprolactone polyol charged, preferably from 0.5 to 2
moles.
Illustrative of polycaprolactone polyols that can be used as
starting materials in this invention one can mention the reaction
products of a polyhydroxyl compound having from 1 to 4 hydroxyl
groups with caprolactone. The manner in which these caprolactone
polyol compositions are produced is shown in U.S. 3,169,945 and
many such compositions are commercially available. In the following
table there are listed illustrative polycaprolactone polyols. The
first column lists the organic functional initiator that is reacted
with the caprolactone and the average molecular weight of the
polycaprolactone polyol is shown in the second column. Knowing the
molecular weights of the initiator and of the polycaprolactone
polyol one can readily determine the average number of molecules of
caprolactone (CPL Units) that reacted to produce the compound; this
figure is shown in the third column.
______________________________________ POLYCAPROLACTONE POLYOLS
Average Average molecular No. of CPL weight of units in Initiator
polyol molecules ______________________________________ 1. Methanol
146 1 2. Methanol 602 5 3. Methanol 2,312 20 4. Ethanol 160 1 5.
Ethanol 4,640 40.3 6. Propanol 1,428 12 7. Isopropanol 573 4.5 8.
Isopropanol 858 7 9. Isopropanol 1,827 15.5 10. Hexanol 786 6 11.
2-ethylhexanol 1,042 8 12. Decanol 1,868 15 13.
2,6,8-trimethyl-i-nonanol 528 3 14. Stearylalcohol 1,125 7.5 15.
Benzylalcohol 1,134 9 16. Benzylcarbinol 578 4 17. o-Tolylcarbinol
863 6.5 18. Cycolhexanol 727 5.5 19. Ethylene glycol 290 2 20.
Ethylene glycol 803 6.5 21. ethylene glycol 2,114 18 22. Propylene
glycol 874 7 23. Octylene glycol 602 4 24. Decalene glycol 801 5.5
25. Diethylene glycol 530 3.7 26. Diethylene glycol 850 6.5 27.
Diethylene glycol 1,246 10 28. Diethylene glycol 2,000 16.6 29.
Diethylene glycol 3,356 30 30. Triethylene glycol 754 5.3 31.
Polyethylene glycol (MW 200).sup.1 713 4.5 32. Polyethylene glycol
(MW 600).sup.1 1,396 7 33. Polyethylene glycol (MW 1,550).sup.1
2,818 12 34. 1,2-propylene glycol 646 5 35. 1,3-propylene glycol
988 8 36. Dipropylene glycol 476 3 37. Polypropylene glycol (MW
425).sup.1 824 3.5 38. Polypropylene glycol (MW 1,004).sup.1 1,688
6 39. Polypropylene glycol (MW 2,000).sup.1 2,456 4 40. Hexylene
glycol 916 7 41. 2-ethyl-1,3-hexanediol 602 4 42. 1,5-pentanediol
446 3 43. 1,4-cyclohexanediol 629 4.5 44.
1,3-bis(hydroxyethyl)-benzene 736 5 45. Glycerol 605 4. 46.
1,2,6-hexanetriol 476 47. Trimethylolpropane 590 48.
Trimethylolpropane 761 5.4 49. Trimethylolpropane 1,133 8.5 50.
Triethanolamine 890 6.5 51. Erythritol 920 52. Pentaerythritol
1,219 9.5 ______________________________________ .sup.1 Average
molecular weight of glycol.
The structures of the compounds in the above tabulation are obvious
to one skilled in the art based on the information given. The
structure of compound No. 6 is: ##STR25## The structures of
compound No. 25 is: ##STR26## wherein the variable r is an integer,
the sum of r+r has an average value of 4.3 and the average
molecular weight is 527. The structure of compound No. 38 is:
##STR27## wherein the sum of r+r has an average value of 6 and the
average molecular weight is 1595. This explanation makes explicit
the structural formulas of compounds 1 to 52 set forth above.
The acrylate-capped polycaprolactone compounds of Formulas I to IV
inclusive can be illustrated by the following compounds. This
tabulation is illustrative only and is not to be considered a
complete tabulation of all possible compounds since other compounds
are obvious in view of applicants' teachings.
__________________________________________________________________________
CH.sub.2CHCOO(CH.sub.2).sub.5 COOCH.sub.3
CH.sub.2CHCO[O(CH.sub.2).sub.5 CO].sub.6 OC.sub.4 H.sub.9 ##STR28##
CH.sub.2CHCO[O(CH.sub.2).sub.5 CO].sub.6 OC.sub.18 H.sub.37
CH.sub.2CHCO[O(CH.sub.2).sub.6 CO].sub.2 OCH.sub.2 CH.sub.2
CHCH.sub.2 ##STR29## ##STR30## ##STR31## ##STR32## ##STR33##
##STR34## (CH.sub.2CHCOO(CH.sub.2).sub.5 COO).sub.2 C.sub.2 H.sub.4
(CH.sub.3CHCO[O(CH.sub.2).sub.5 CO].sub.r O).sub.2 C.sub.2 H.sub.4
(average of r is 4) ##STR35## ##STR36##
(CH.sub.2CHCO[O(CH.sub.2).sub.5 CO].sub.r O).sub.2 C.sub.10
H.sub.30 (average of r is 6) (CH.sub.2CHCO[O(CH.sub.2).sub.5
CO].sub.r O).sub.2 C.sub.2 H.sub.4 OC.sub.2 H.sub.4 (average of r
is 4.3) ##STR37## (CH.sub.2CHCO[O(CH.sub.2).sub.5 CO].sub.r
O).sub.2 H.sub.4 OC.sub.2 H.sub.4 (average of r is 35)
(CH.sub.2CHCO[O(CH.sub.2).sub.5 CO].sub.r O).sub.2 (C.sub.2 H.sub.4
O).sub.12.6 C.sub.2 H.sub.4 (average of r is 4,5) ##STR38##
##STR39## ##STR40## (CH.sub.2CHCO[O(CH.sub.2).sub.5 CO].sub.r
OCH.sub.2).sub.3 CCH.sub.2 CH.sub.3 (average of r is 4) ##STR41##
CH.sub.2CHCO[O(CH.sub.2).sub.5 CO].sub.r OC.sub.3 H.sub.4
O[OC(CH.sub.2).s ub.5 O].sub.r H (average of r is 3,5)
CH.sub.2CHCO[O(CH.sub.2).sub.5 CO].sub.r OC.sub.2 H.sub.4 OC.sub.2
H.sub.4 O[OC(CH.sub.2).sub.5 O].sub.r H (average of r is 5)
CH.sub.2CHCO[O(CH.sub.2).sub.5 CO].sub.r O(C.sub.2 H.sub.4
O).sub.10 [O(CH.sub.2).sub.4 O].sub.r H (average of r is 6)
CH.sub.2CHCO[O(CH.sub.2).sub.5 CO].sub.r OC.sub.2 H.sub.4
O[OC(CH.sub.2).s ub.5 O].sub.r OCH (average of r is 4)
CH.sub.2CHCO[O(CH.sub.2).sub.5 CO].sub.r OC.sub.2 H.sub.4 OC.sub.2
H.sub.4 O[OC(CH.sub.2).sub.5 O].sub.r OCCH.sub.3 (average of r is
3.5) CH.sub.2CHCO[C(CH.sub.3).sub.5 CO].sub.r OC.sub.10 H.sub.20
O[OC(CH.sub.2) .sub.6 O].sub.r OCC.sub.4 H.sub.13 (average of r is
5) ##STR42## ##STR43## (CH.sub.2CHCO[O(CH.sub.2).sub.5 CO].sub.r
OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 O[OC(CH.sub.2).sub.5 O].sub.r
OC).sub.2 (average of r is 3,5) (CH.sub.2CHCO[O(CH.sub.2).sub.5
CO].sub.r OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 O[OC(CH.sub.2).sub.5
O].sub.r OC).sub.2 C.sub.4 H.sub.2 (average of r is 4) ##STR44##
CH.sub.2CHCO[O(CH.sub.2).sub.5 CO].sub.r OC.sub.2 H.sub.4
O[OC(CH.sub.2).s ub.4 O].sub.r OCNHCH.sub.3 (average of r is 7,6)
##STR45## (CH.sub.2CHCO[O(CH.sub.2).sub.5 CO].sub.r OC.sub.2
H.sub.4 O[OC(CH.sub.2). sub.6 O].sub.r OCNH).sub.2 C.sub.5 H.sub.12
(average of r is 4) ##STR46## ##STR47## ##STR48## ##STR49##
(CH.sub.2CHCOOC.sub.2 H.sub.16 OOCNHC.sub.4 H.sub.12
NHCO[O(CH.sub.2).sub. 5 CO].sub.r O).sub.2 C.sub.3 H.sub.4 (average
of r is 6) ##STR50## ##STR51## ##STR52## 20/20 mixture of tolylene
diisocyanates ##STR53## ##STR54## ##STR55## ##STR56## ##STR57##
##STR58## ##STR59## ##STR60## ##STR61##
__________________________________________________________________________
In the above compounds the term "average of r" means the average
value of the total sum of all of the r variables in the
compound.
In carrying out the processes for producing the acrylate-capped
polycaprolactone compounds an inert gas atmosphere can be used,
however, this is not essential for the process.
(2) The coating compositions
The acrylate-capped polycaprolactone compounds can be used per se
as coating compositions, either alone or in admixture with
conventional solvents, pigments, fillers and other additives. They
can be applied by conventional means and cured by exposure to heat,
light, electron radiation, X-ray radiation, and other known means
for curing and crosslinking a polymer, either alone or in the
presence of a crosslinker.
The acrylate-capped polycaprolactone polyols can also be used to
produce coating compositions known as 100 percent solids coating
compositions by mixing with a reactive solvent. These reactive
solvents are well known to those skilled in the art and include
olefinic monomers such as styrene, alpha-methyl styrene, and
acrylyl compounds such as the acrylate esters, the methacrylate
esters, the acrylamides and the methacrylamides. These acrylyl
compounds can be represented by the formula: ##STR62## wherein Z is
hydrogen or methyl; t is an integer having a value of 1 or 2; and
R'" is alkoxy having from 1 to about 18 carbon atoms (e.g.,
methoxy, ethoxy, propoxy, isopropoxy, 2-methylhexoxy,
2-ethylhexoxy, decoxy, octadecoxy); hydroxyalkoxy having up to
about 15 carbon (e.g., hydroxymethoxy, hydroxyethoxy,
hydroxypropoxy, hydroxydecoxy); alkoxyalkoxy having up to a total
of about 15 carbon atoms (e.g., methoxymethoxy, methoxyethoxy,
ethoxybutoxy, methoxypropoxy, decoxypentoxy); cyano; cyanoalkoxy
having up to about 15 carbon atoms (e.g., cyanomethoxy,
cyanobutoxy, cyanodecoxy); aryloxy (e.g., phenoxy, toloxy, xyloxy,
phenoxyethoxy, naphthoxy, benzyloxy); or an --(OC.sub.n
H.sub.2n).sub.z NR" ".sub.2 group wherein n is an integer having a
value of 1 to 10, z has a value of 0 or 1 and R" " is alkyl having
1 to 10 carbon atoms when t is one or divalent alkylene or
oxyalkylene having 2 to 8 carbon atoms in the alkylene moiety
thereof when t is two.
Illustrative of suitable acrylyl compounds, many more of which are
well known in the art, one can mention methyl acrylate, ethyl
acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl
acrylate, butyl acrylate, methoxybutyl acrylate, cyano acrylate,
cyanoethyl acrylate, phenyl acrylate, methyl methacrylate, propyl
methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate,
phenyl methacrylate, ethyl methacrylate, lauryl methacrylate,
N,N-dimethyl acrylamide, N,N-diisopropyl acrylamide, N,N-didecyl
acrylamide, N,N-dimethyl methacrylamide, N,N-diethyl
methacrylamide, (N,N-dimethylamino)methyl acrylate,
2-(N,N-dimethylamino) ethyl acrylate, 2-(N,N-dipentylamino)ethyl
acrylate, N,N-dimethylamino)methyl methacrylate,
2-(N,N-diethylamino)propyl acrylate, ethylene glycol diacrylate,
propylene glycol diacrylate, neopentyl glycol diacrylate,
1,6-hexanediol diacrylate, diethylene glycol diacrylate,
triethylene glycol diacrylate, dipropylene glycol diacrylate,
ethylene glycol diacrylate, ethylene glycol dimethacrylate,
propylene glycol dimethacrylate, diethylene glycol dimethacrylate,
tripropylene glycol diacrylate, and the like.
The coating compositions can contain from about 0.1 to about 10
weight percent of any activator such as any of the known
photosensitizers or photoinitiators, preferably from about one to
about 5 weight percent. These can be used singly or in mixtures and
include, for example, benzophenone, p-methoxybenzophenone,
acetophenone, m-chloroactophenone, propiophenone, xanthone,
benzoin, benzil, benzaldehyde, naphthoquinone, anthraquinone,
di-t-butyl peroxide, dicumyl peroxide, t-butyl hydroperoxide,
t-butyl peracetate, peracetic acid, perbenzoic acid, benzoyl
peroxide, dichlorobenzoyl peroxide, azobis(isobutyronitrile),
dimethyl azobis(isobutyrate), morpholine, diethylamine, piperidine,
pyrrolidine, and the like.
Thus, the coating compositions can contain from 10 to 100 weight
percent of the acrylate-capped polycaprolactone compound of
Formulas I to IV inclusive, with from 40 to 95 weight percent
preferred, and from about 50 to 85 weight percent being most
preferred. The concentration of reactive solvent can be from zero
to about 90 weight percent, with from 5 to 60 weight percent
preferred, and from 10 to 50 weight percent most preferred.
The coating compositions are produced by conventional methods by
mixing the selected components together. To facilitate preparation
one can apply a small amount of heat. The coatings can be applied
by conventional means, including spray, curtain, dip, pad,
roll-coating and brushing procedures. They may, if desired, be
dried under ambient or oven conditions. The coatings can be applied
to any acceptable substrate such as wood, metal, glass, fabric,
paper, fiber, plastic that is in any form, e.g., sheet, coil,
molded, film, panel, tube, etc.
The coating compositions containing acrylate-capped
polycaprolactone compounds can be cured by exposure to heat or
radiation, either before or after the coating has dried. The
radiation can be ionizing radiation, either particulate or
non-particulate or non-ionizing radiation. As a suitable source of
particulate radiation, one can use any source which emits electrons
or charged nuclei. Particulate radiation can be generated from
electron accelerators such as the Van de Graaff accelerator,
resonance transformers, linear accelerators, insulating core
transformers, radioactive elements such as cobalt-60 strontium-90,
etc. As a suitable source of non-particulate ionizing radiation,
one can use any source which emits radiation in the range of from
about 10.sup.-.sup.3 angstroms, to about 2000 angstroms, preferably
from about 5.times.10.sup.-.sup.3 angstroms to about 1 angstrom.
Suitable sources are vacuum ultraviolet lamps, such as xenon or
krypton arcs, and radioactive elements such as cesium-137,
strontium-90, and cobalt-60. The nuclear reactors are also known to
be a useful source of radiation. As a suitable source of
non-ionizing radiation, one can use any source which emits
radiation of from about 2000 angstroms to about 4000 angstroms.
Suitable sources are mercury arcs, carbon arcs, tungsten filament
lamps, xenon arcs, krypton arcs, sunlamps, lasers, and the like.
All of these devices and sources are well known in the art and
those skilled in radiation technology are fully aware of the manner
in which the radiation is generated and the precautions to be
exercised in its use.
The use of low to high pressure mercury lamps to generate
ultraviolet light is known. The largest such mercury lamp of
commercial utility is generally about five feet long having a
diameter of about one to two inches with an electrical input of
about 20 kilowatts generating a typical low intensity ultraviolet
light line structure (source intensity is generally no greater than
about 20 kilowatts per square foot of source projected area). An
appreciable period of time is generally needed for completion of a
reaction when a material is exposed to the low intensity
ultraviolet radiation generated from a mercury lamp.
The ionizing radiation dosage necessary to effect curing or
crosslinking will vary depending upon the composition of the
particular coating that is undergoing radiation, the extent of
crosslinking desired, the number of crosslinkable sites available
and the molecular weight of the starting polymer in the coating
composition. The total dosage will be from about 10.sup.3 rads to
10.sup.8 rads, preferably from 5.times.10.sup.3 rads to 10.sup.7
rads. A rad is 100 ergs of ionizing energy absorbed per gram of
material being irradiated.
Recently a source of light radiation emitting high intensity
predominantly continuum light radiation containing ultraviolet,
visible and infrared radiation that can be used to polymerize
monomers and to crosslink polymer compositions was discovered,
namely the swirl-flow plasma arc radiation source. By means of
proper light filters one can selectively screen out a portion of
the light radiation emitted, permitting only that wavelength
portion desired to reach the material being treated.
The term "high intensity predominantly continuum light radiation"
means continuum radiation with a radiance or source intensity of at
least 350 watts per square centimeter steradian (about 1000
kilowatts per square foot of source projected area) having only a
minor part of the energy in peaks of bandwidths less than 100
Angstrom units, with less than about 30 percent of the light
radiated having wavelengths shorter than 4,000 angstrom units and
at least about 70 percent of the light energy radiated having
wavelengths longer than 4,000 angstrom units.
This light radiation is derived from an artificial source that
generates high intensity predominantly continuum light radiation
with a source intensity of at least about 350 watts per square
centimeter steradian, as abbreviated by the term: watts
cm..sup.-.sup.2 sr.sup.-.sup.1 ; said high intensity predominantly
continuum artificial light radiation has about 70 percent of the
light radiated at a wavelength longer than 4,000 angstroms and less
than about 30 percent of the light radiated having a wavelength
shorter than 4,000 angstroms, generally about 80 percent of the
light radiated has a wavelength longer than 4,000 angstroms and
less than about 20 percent of the light radiated has a wavelength
shorter than 4,000 angstroms, and a source intensity that can vary
from about 350 watts (about 1000 kilowatts per square foot of
source projected area) to about 5,000 watts (about 15,000 kilowatts
per square foot of source projected area) or more per square
centimeter steradian. A convenient source of high intensity
predominantly continuum light radiation is a swirl-flow plasma arc
light radiation apparatus. The equipment for generating high
intensity predominantly continuum light radiation by this means is
known and available; many different forms thereof are described in
the literature. A highly efficient apparatus for obtaining high
intensity predominantly continuum light radiation is the swirl-flow
plasma arc radiation source described in U.S. 3,364,387. The
apparatus or equipment necessary for generating the light radiation
is not the subject of this invention and any source or apparatus
capable of generating high intensity predominantly continuum light
radiation can be used.
While any artificial source of generating high intensity
predominantly continuum light radiation can be used, as previously
indicated the swirl-flow plasma arc radiation apparatus is most
convenient. Hence, this source will be used in this application as
illustrative of a means for obtaining the high intensity
predominantly continuum light radiation. Any apparatus that
operates according to the known principles of the swirl-flow plasma
arc radiation source can be used to produce the high intensity
predominantly continuum light radiation useful in the processes of
this invention. These apparatuses are often known by other terms
but those skilled in this art recognize that they emit high
intensity predominantly continuum light radiation. The source of
radiation in a 50 kilowatt swirl-flow plasma arc radiation source
is an arc only about four inches long enclosed in a quartz envelope
about 1.5 inches in diameter. This lamp can be readily removed and
refurbished and has an acceptable long lifetime. Further, a
swirl-flow plasma arc radiation apparatus having a 250-kilowatt
rating would be only about two or three times as large as a
50-kilowatt source. Another advantage is the absence of a need for
expensive radiation shielding. Precautions required for the
artificial light sources include those needed to protect one's eyes
from the intense visible light and from the ultraviolet light
present to prevent inadvertent sunburn effect on the body.
It is to be noted that in the spectra of high intensity
predominantly continuum light radiation there is a continuum of
radiation throughout the entire spectral range. This type of
continuum radiation in the ultraviolet range has not heretofore
been obtainable from the conventional commercial mercury arcs of
lamps generally available for generating ultraviolet light. The
previously known means for generating ultraviolet light produced
light that shows a line or peak spectrum in the ultraviolet range,
it is not a continuum spectrum in the ultraviolet range. In a line
spectrum the major portion of usesble ultraviolet light is that
portion at which the line or band in the spectrum forms a peak; in
order for such energy to be useful the material or composition that
is to be treated with ultraviolet radiation must be capable of
absorbing at that particular wavelength range at which the peak
appears. In the event the material or composition does not have the
ability to absorb at that particular wavelength range there is
little or no absorption or reaction. Thus, in the event the
material or composition to be treated absorbs at a particular
wavelength range in one of the valleys of the spectral curve there
will be little or no reaction since there is little or no
ultraviolet energy to adequately excite the system. With a high
intensity predominantly continuum radiation, there is a high
intensity continuum radiation of ultraviolet energy across the
entire ultraviolet wavelength range of the spectrum and there is
generally sufficient ultraviolet energy generated at all useful
ultraviolet wavelengths to enable one to carry out reactions
responsive to ultraviolet radiation without the problem of
selecting compounds that will absorb at the peak wavelength bands
only. With the high intensity continuum radiation now discovered
one does not have the problem of being unable to react materials or
compositions that absorb in the valley areas only since for all
intents and purposes such valleys do not exist in high intensity
continuum radiation, the high intensity radiated light energy is
essentially a continuum, it is not in peak bands.
High intensity predominantly continuum light radiation is to be
distinguished from low intensity ultraviolet radiation generated by
commercially available low, medium and high pressure mercury arc
ultraviolet lamps. These mercury arc lamps produce light emission
which is primarily line or peak rather than continuum light,
wherein a major part of the light appears in bands narrower than
100 angstrom units, and much less than 70 percent is above 4,000
angstrom units.
As is known, high intensity predominantly continuum light radiation
from a swirl-flow plasma arc radiation source is emitted from an
arc generated between a pair of electrodes that are lined up
axially and encased in a quartz cylinder. In an embodiment a pair
of concentric quartz cylinders between which cooling water or gas
flows is used. A rare gas, such as argon, krypton, neon or xenon,
introduced into the inner cylinder tangentially through inlets
located at one end of the inner cylinder creates a swirling flow or
vortex which restricts the arc to a small diameter. An electrical
potential applied across the electrodes causes a high density
current to flow through the gas to generate a plasma composed of
electrons, positively charged ions and neutral atoms. A plasma
generated in the above gases produces high intensity predominantly
continuum light radiation with diffuse maxima in the region of from
about 3,500 to about 6,000 angstroms. The radiation source can also
be used with reflectors or refractive optical systems to direct the
high intensity predominantly continuum light radiation emanating
from the arc to a particular point or direction or geometrical
area.
The acrylate-capped polycaprolactone compositions are readily cured
by exposure to the predominantly continuum light radiation for a
short period of time. The exposure can vary from a period as short
as a fraction of a second to a period that may be as long as ten
minutes or longer. In most instances a period of from about 0.1
second to about two minutes is adequate. The distance of the
acrylate-capped polycaprolactone composition from the arc source
can vary from a fraction of an inch up to 10 feet or more;
preferably the distance is from about one foot to about 4 feet.
Exposure can be under normal atmospheric conditions or under an
inert gas blanket, for example under nitrogen; the preferred
process is to use an inert gas atmosphere.
ILLUSTRATIVE EXAMPLES
EXAMPLE 1
A polycaprolactone polyol (98 grams), produced as described in U.S.
3,169,945 by the reaction of diethylene glycol and
epsilon-caprolactone and having an average molecular weight of
about 530, was placed in a 500 ml. flask that was equipped with a
stirrer, thermocouple and two dropping funnels. After the addition
of one drop of dibutyltin dilaurate the mixture was heated to
80.degree. C. in an oil bath and 128 grams of
bis(2-isocyanatoethyl)5-norbornen-2,3-dicarboxylate and 52 grams of
2-hydroxypropyl acrylate were co-fed in a dropwise manner while
stirring vigorously. The addition of the hydroxypropyl acrylate was
completed in two hours; thereafter the mixture was stirred for an
additional one-half hour at 80.degree. C. The acrylate-capped
polycaprolactone urethane produced had the basic structure:
##STR63## This product was a clear, straw yellow liquid. A solution
containing 73 weight percent of the acrylate-capped
polycaprolactone and 27 weight percent of 2-butoxyethyl acrylate
had a Brookfield viscosity of 1,780 cps. at 23.degree. C.
In a similar manner the acrylate-capped polycaprolactone of the
following structure is produced by the use of 2-hydroxyethyl
methacrylate and a polycaprolactone polyol having an average
molecular weight of about 786 that was produced by the reaction of
hexanol and epsiloncaprolactone ##STR64##
EXAMPLE 2
A solution of 98 grams of the polycaprolactone polyol used in
Example 1, 52 grams of 2-hydroxypropyl acrylate and one drop of
dibutyltin dilaurate was heated to 70.degree. C. The solution was
stirred while 69.6 grams of an 80/20 mixture of 2,4- and
2,6-tolylene diisocyanates was added in a dropwise manner over a
period of two hours. The mixture was stirred for an additional
one-half hour and then 0.002 gram of 4-methoxyphenol was added as a
stabilizer. The acrylate-capped polycaprolactone urethane produced
had the basic structure: ##STR65## This product was a clear liquid.
A solution containing 73 weight percent of the acrylate-capped
polycaprolactone and 27 weight percent of 2-butoxyethyl acrylate
had a Brookfield viscosity of 2,270 cps. at 23.degree. C.
Example 3
In a method similar to that described in Example 1, a solution of
98 grams of the same polycaprolactone polyol, 73.2 grams of
2-butoxyethyl acrylate as solvent, one drop of dibutyltin dilaurate
and 0.01 gram of 4-methoxyphenol was heated to 70.degree. C. and
69.6 grams of an 80/20 mixture of 2,4- and 2,6-tolylene
diisocyanate and 52 grams of 2-hydroxypropyl acrylate were
simultaneously co-fed as separate streams over a period of two
hours. The mixture was stirred an additional one-half hour at
65.degree. C. The light yellow solution of the acrylate-capped
polycaprolactone urethane had a Brookfield viscosity of 20,000 cps.
at 23.degree. C.
EXAMPLE 4
A solution containing 98 grams of the same polycaprolactone polyol
used in Example 1, 52 grams of 2-hydroxypropyl acrylate, 81.2 grams
of 2-butoxyethyl acrylate and one drop of dibutyltin dilaurate was
heated to 70.degree. C. and then 69.6 grams of an 80/20 mixture of
2,4- and 2,6-tolylene diisocyanates were added in a dropwise manner
over a period of about two hours. The reaction mixture was stirred
another half-hour at about 70.degree. C. and then 0.002 gram of
4-methoxyphenol was added. The solution of the acrylate-capped
polycaprolactone urethane had a Brookfield viscosity of 13,600 cps.
at 23.degree. C.
The acrylate-capped polycaprolactone polymer produced in Examples 3
and 4 had the same basic structure as the polymer produced in
Example 2.
EXAMPLE 5
In a method similar to that described in Example 1, 128 grams of
bis(2-isocyanatoethyl)5-norbornen-2,3-dicarboxylate and a mixture
of 46.4 grams of 2-hydroxyethyl acrylate containing 0.005 gram of
4-methoxyphenol were simultaneously co-fed to a mixture of 98 grams
of the same polycaprolactone polyol and one drop of dibutyltin
dilaurate and reacted as described in Example 1. The
acrylate-capped polycaprolactone urethane was light yellow and had
the basic structure: ##STR66## A solution was prepared containing
73 weight percent of the acrylate-capped polycaprolactone and 27
weight percent of 2-butoxyethyl acrylate; it had a Brookfield
viscosity of 2,800 cps. at 23.degree. C.
EXAMPLE 6
In a method similar to that described in Example 4, 69.6 grams of
an 80/20 mixture of 2,4- and 2,6-tolylene diisocyanates was added
to a solution of 98 grams of the polycaprolactone polyol used in
Example 1, 46.4 grams of 2-hydroxylethyl acrylate, 0.005 gram of
4-methoxyphenol, 79.2 grams of 2-butoxyethyl acrylate and one drop
of dibutyltin dilaurate. The solution of acrylate-capped
polycaprolactone urethane resin that was produced had a Brookfield
viscosity of 2,100 cps. at 23.degree. C. The resin had the basic
structure: ##STR67##
EXAMPLE 7
In a method similar to that described in Example 1, 69.6 grams of
an 80/20 mixture of 2,4- and 2,6-tolylene diisocyanates and a
mixture of 46.4 grams of 2-hydroxyethyl acrylate and 0.005 gram of
4-methoxyphenol were simultaneously co-fed to a solution of 98
grams of the same polycaprolactone polyol used in Example 1, 79.2
grams of 2-butoxyethyl acrylate and one drop of dibutyltin
dilaurate. The solution of acrylate-capped polycaprolactone
urethane produced had a Brookfield viscosity of 6,750 cps. at
23.degree. C. The resin had the same basic structure shown in
Example 6.
EXAMPLE 8
In a method similar to that described in Example 4, 104.4 grams of
an 80/20 mixture of 2,4- and 2,6-tolylene diisocyanate and a
mixture of 69.6 grams of 2-hydroxyethyl acrylate containing 0.007
gram of 4-methoxyphenol were simultaneously co-fed to a solution of
106.8 grams of a polycaprolactone polyol that had an average
molecular weight of about 530, 82.4 grams of 2-butoxyethyl acrylate
and one drop of dibutyltin dilaurate. The polycaprolactone polyol
was the reaction product of trimethylolpropane and
epsiloncaprolactone. The addition and reaction was carried out at
about 65.degree. C. The resin had the basic structure:
##STR68##
EXAMPLE 9
In a method similar to that described in Example 1, 104.8 grams of
methylenebis(4-isocyanatophenyl) and 46.4 grams of 2-hydroxy-ethyl
acrylate were simultaneously co-fed over a period of three hours to
a solution of 98 grams of the polycaprolactone polyol used in
Example 1, 92.2 grams of 2-butoxyethyl acrylate and one drop of
dibutyltin dilaurate. The light yellow solution containing the
acrylate-capped polycaprolactone urethane polymer had a Brookfield
viscosity of 16,900 cps. at 23.degree. C. The polymer had the basic
structure: ##STR69##
EXAMPLE 10
A solution of 213.6 grams of the polycaprolactone polyol used in
Example 8, 146.2 grams of 2-hydroxyethyl acrylate, one drop of
dibutyltin dilaurate, 0.015 gram of 4-methoxyphenol and 142.2 grams
of 2-butoxyethyl acrylate was heated to 65.degree. C. Over a period
of two hours, 208.8 grams of an 80/20 mixture of 2,4- and
2,6-tolylene diisocyanates was added and the solution was stirred
an additional nine hours at 65.degree. C. The solution contained 80
weight percent of acrylate-capped polycaprolactone urethane resin
having the same basic structure as the product of Example 8.
Additional 2-butoxyethyl acrylate was added to dilute the solution
to a 55 weight percent content of acrylate-capped polycaprolactone
resin. This diluted solution had a Brookfield viscosity of 1,950
cps. at 23.degree. C.
EXAMPLE 11
A series of acrylate-capped polycaprolactone resins was prepared.
In these reactions the polycaprolactone polyol, the 2-butoxyethyl
acrylate, one drop of dibutyltin dilaurate and the 2-hydroxyethyl
acrylate were placed in brown bottles. To these solutions there was
added the 80/20 mixture of 2,4- and 2,6-tolylene diisocyanates over
a period of one to two hours, vigorously shaking after each
addition. The capped bottles were left in an oven at 60.degree. C.
for 16 hours. The Brookfield viscosities were determined on 80
percent solution of the acrylate-capped polycaprolactone resins in
2-butoxyethyl acrylate. The 2-hydroxyethyl acrylate contained 40
parts per million of 4-methoxyphenol.
__________________________________________________________________________
Run A B C D E F G H
__________________________________________________________________________
PCP, type I I I I II II II II PCP,g 48.8 39.3 28.3 15.4 38.0 29.4
20.3 10.5 BEA,g 11.1 11.1 11.1 11.1 11.1 11.1 11.1 11.1 HEA,g 21.1
28.4 36.8 46.6 25.6 33.0 41.0 49.4 TDI,g 30.1 32.3 34.9 38.0 36.4
37.6 38.8 40.2 Viscosity, cps 9,920 5,960 4,980 3,460 111,000
34,000 15,700 3,400
__________________________________________________________________________
PCP-I=polycaprolactone polyol of Example 1. PCP-II=polycaprolactone
polyol of Example 8. BEA=2-butoxyethylacrylate.
HEA=2-hydroxyethylacrylate. TDI=tolylene diisocyanate.
EXAMPLE 12
A series of acrylate-capped polycaprolactone resins was prepared in
a manner similar to that described in Example 11. The tolylene
diisocyanate was added in five milliliter increments over a period
of about two hours. Thereafter the bottles were capped, allowed to
stand at room temperature for 24 hours, and then left in an oven at
60.degree. C. for 16 hours. The amounts of reactants charged and
the Brookfield viscosities at 23.degree. C. of a 60 weight percent
solution of the resin in the acrylate solvents are set forth
below:
______________________________________ Run A B C D
______________________________________ PCP-II,g 26.7 21.4 32.0 26.7
EEA,g 28.4 29.8 31.1 BA,g 28.4 HEA,g 18.6 21.9 14.6 18.6 TDI,g 26.1
26.1 26.1 26.1 Viscosity, cps 1,630 650 4,650 1,170
______________________________________ PCP-II=polycaprolactone
polyol of Example 8. EEA=2-ethoxyethyl acrylate. BA=butyl acrylate
HEA=2-hydroxyethyl acrylate. TDI=tolylene diisocyanate.
EXAMPLE 13
A mixture of 271 grams of the polycaprolactone polyol used in
Example 1, 7,017 grams of glacial acrylic acid and 50 cc. of
benzene was heated in a flask until a homogeneous solution was
obtained. Nitrogen was bubbled through the mixture during the
entire reaction. After solution was achieved, 0.8 percent of
sulfuric acid catalyst and 0.1 percent of phenothiazine were added
and the solution was maintained at a steady reflux at 80.degree. C.
to 95.degree. C. until amost of the water of reaction had distilled
over. The reaction mixture was cooled to room temperature and 6
grams of calcium hydroxide was added to neutralize the sulfuric
acid and the unreacted excess acrylic acid. It was then filtered,
stripped of benzene, and dried over molecular sieves. This
acrylate-capped polycaprolactone had the basis structure:
EXAMPLE 14
To a portion of the acrylate-capped polycaprolactone of Example 13
there was added five weight percent of an 80/20 mixture of 2,4- and
2,6-tolylene diisocyanates. This mixture was reacted at 60.degree.
C. to produce a mixture of the urethane oligomer having the basic
structure which is indicated below and the acrylate-capped
polycaprolactone of Example 13. ##STR70## (sum of a and b has a
total average value of 3.7).
EXAMPLE 15
There were charged to a one liter flask 200 grams of the
polycaprolactone polyol of Example 8, 400 ml. of benzene and 0.25
ml. of dibutyltin dilaurate and the mixture was stirred to
solution. Over a thirty minute period 176.1 grams of
bis(2-isocyanatoethyl)-5-norbornen-2,3-dicarboxylate were added at
about 15.degree. C. to about 25.degree. C. Then the reaction
mixture was stirred at 50.degree. C. for about one hour and ten
minutes at which time 113.4 grams of 2-hydroxypropyl acrylate,
containing 0.003 gram of 4-methoxyphenol were added and the
solution was allowed to stand overnight at room temperature. There
were obtained 825.2 grams of a benzene solution of the
acrylate-capped polycaprolactone resin, the solution having a total
solids content of 54.45 percent. The reduced viscosity at
30.degree. C. of a 0.5 percent solution of acrylate-capped
polycaprolactone resin in benzene was 0.043 dl./gm.
EXAMPLE 16
A series of coating compositions was produced by mixing the
acrylate-capped polycaprolactone resins of Examples 1 to 4 with
different acrylyl compounds, as indicated in the following table.
The liquid compositions were used to coat steel panels using a
number three wire-wound rod. The coatings were cured by exposure of
the wet film to electrons generated by a 300 kilovolt electron
accelerator. The results are set forth below:
__________________________________________________________________________
Coating composition A B C D E F
__________________________________________________________________________
Resin, source, Ex 1 2 3 3 4 4 Parts 73 56.2 73 56.2 63 56.2 Acrylyl
compound, parts: BEA 27 18.7 27 18.7 26 18.7 EHA 18.2 18.2 18.2
NPGDA 6.9 6.9 6.9 DEGDA 11 Brookfield viscosity, cps. at 1,780 800
20,000 1,940 13,600 1,499 23.degree. C. Dose to cure, megarads 8 24
16 16 16 16 Sward hardness, glass=100 26 30 16 16 16 14 Reverse
impact, in. lb Greater than 165 Adhesion (post-irradiation):
Cross-hatch E E E P G E Impacted bump P G P P P G Burr/edge F E E P
P E Adhesion (post-pasteurization): Cross-hatch P F P P P P
Burr/edge P E P P P P
__________________________________________________________________________
E=excellent; G=good; F=fair; P=poor. BEA=2-butoxyethyl acrylate.
EHA=2-ethylhexyl acrylate. NPGDA=neopentyl glycol diacrylate.
DEGDA=diethylene glycol diacrylate.
EXAMPLE 17
The compositions of Runs A to H of Example 11 were coated on steel
panels and cured in air by the procedure described in Example 16.
The coatings were given a total radiation dosage of four megarads.
In those instances in which a slightly tack film was obtained after
this treatment, continued radiation will eliminate the
tackiness.
__________________________________________________________________________
Coating composition 1 2 3 4 5 6 7 8
__________________________________________________________________________
Resin source, Example 11, A B C D E F G H Run. Sward hardness,
glass=100 6 6 6 6 12 22 26 18 Reverse impact, in lb. >165
>165 20 5 30 5 5 18 Film condition .sup.(1) .sup.(1) .sup.(1)
.sup.(1) .sup.2 .sup.(2) .sup.(2) .sup.(1)
__________________________________________________________________________
.sup.1 Sl. tack. .sup.2 Cured.
EXAMPLE 18
The compositions of Runs A to G of Example 11 were diluted with
sufficient 2-ethoxy-ethyl acrylate to obtain diluted compositions
having Brookfield viscosities at 23.degree. C. of 250.+-.50 cps.
Three mil thick coatings were made on steel panels and cured in air
by the procedure described in Example 16. The results are tabulated
below.
__________________________________________________________________________
Coating composition 1 2 3 4 5 6 7
__________________________________________________________________________
Resin source, Example 11, Run A B C D E F G Dose to cure, megarads
10 10 10 8 6 4 4 Sward hardness, glass=100 10 14 14 18 18 24 16
Reverse impact, in lb. Greater than 165 Adhesion
(post-irradiation): Cross hatch P P P E E E F Impacted bump P P P F
F E F Burr edge E E E E E E E Adhesion (post-pasturization): Cross
hatch E P P P E E F Burr edge E P E P F E F
__________________________________________________________________________
EXAMPLE 19
Coating compositions 1 to 7 of Example 18 were cured as described
in Example 18 with the exception that the irradiations were
conducted in a nitrogen atmosphere. The coatings were all cured
after radiation with a dosage of 2 megarads and all had a reverse
impact of more than 165 inch pounds. The results are tabulated in
the following table:
__________________________________________________________________________
Coating composition 1 2 3 4 5 6 7
__________________________________________________________________________
Sward hardness, glass=100 26 36 24 34 22 30 46 Adhesion
(post-irradiation): Cross hatch F F P E E E G Impacted bump P P P G
G G G Burr Edge P E E E E E E Adhesion (post pasteurization): Cross
hatch P P P P P E E Impacted bump P P P P P E E
__________________________________________________________________________
EXAMPLE 20
The compositions of Runs A to H of Example 11 were each blended
with 3 weight percent benzophenone and 2 weight percent
triethanolamine as photosensitizers. The separate blends were
coated on steel panels and the coatings were irradiated with the
predominantly continuum light radiation emanating from a 50
kilowatt argon swirl-flow plasma arc radiation source. Irradiation
was carried out for ten seconds at a distance of two feet from the
arc source; in all instances the films were cured to solid
coatings.
__________________________________________________________________________
Coating composition 1 2 3 4 5 6 7 8
__________________________________________________________________________
Resin source, Example 11, Run A B C D E F G H Sward hardness,
glass=100 10 20 40 72 14 52 72 16 Reverse impact, in lb. 165 165
165 50 65 65 100 20 Adhesion to steel E G F P P F F F
__________________________________________________________________________
When Coating Compositions 1 to 8 of Example 20 were cured by
irradiation with ultraviolet light from a 500 watt medium pressure
mercury arc, a wrinkled, tack-free finish was obtained after a long
exposure of from 300 to 400 seconds.
EXAMPLE 21
A solution of the polycaprolactone polyol (163.4 g.) described in
Example 8, 2-hydroxyethyl acrylate (107.8 g.), 2-ethoxyethyl
acrylate (107.1 g.), and dibutyltin dilaurate (0.1 g.) was placed
in a brown bottle. To this solution was fed portionwise
methylenedi(4-cyclohexylisocyanate) (260.3 g.) After each
incremental addition of the diisocyanate, the bottle was vigorously
agitated and cooled in a water bath. The resulting oligomer, which
has a Brookfield viscosity of about 30,000 cps. at 23.degree. C.,
had the basic structure: ##STR71##
The following procedures were used to test the above
compositions.
Sward hardness--Paint Testing Manual issued by Gardner Laboratory,
Inc., P.O. Box 5728, Bethesda 14, Md., page 138
Reverse impact test--Same as above, p. 146
Adhesion
Crosshatch--conducted by scribing a film with a sharp knife into
101/8" squares, pressing scotch tape firmly against the scribed
surface at 45.degree. angle to the squares and pulling the tape
away with one quick motion. Based on film condition the adhesion is
rated: E (no effect--excellent), G (good--slight effect), F
fair-most of the film remains on the substrate) and P (poor-tape
removes all of the coating from the substrate).
Impacted bump--same as crosshatch on impression resulting from the
reverse impact test.
Burr edge--consists of shearing film and substrate and conducting a
crosshatch test on the unscribed cut-edge.
* * * * *