Vinyl terminated, fully reacted urethane compositions comprise the reaction product of polyisocyanate, an hydroxyalkylated novolac and an ethylenically unsaturated alcohol. The vinyl terminated compositions are copolymerizable with ethylenically unsaturated monomers to produce thermoset polymers characterized by excellent physical properties and a high degree of resistance to acids and alkalies. The polymers are especially useful in the manufacture of molded articles and laminates and in the formulation of marine coatings.

BACKGROUND OF THE INVENTION 
This invention relates to vinyl terminated polyurethane compositions which 
may be copolymerized with ethylenically unsaturated monomers to produce 
thermoset polymers characterized by excellent corrosion resistance and 
high impact strength. 
A variety of corrosion-resistant polymeric materials have been developed 
and used for the manufacture of chemical processing equipment such as 
ducts, pipe, hoods, stacks, processing tanks, storage tanks and the like 
for the handling of corrosive liquids and vapors. Although corrosion 
resistance is a major consideration in the selection of a polymer for such 
purposes, various other factors such as cost, ease of fabrication, 
mechanical strength, thermal stability, and impact resistance must also be 
considered. For example, the rate of failure of prior art corrosion 
resistant polymers through impact or vibration has been a major problem. 
Polyester resins such as those derived from bisphenol A and fumaric acid 
are noted for exceptional thermal and hydrolytic stability and have been 
used extensively in the manufacture of equipment which will withstand 
strong acids and bases, However, such polymers, even when reinforced with 
glass fiber and the like are brittle and tend to crack or fracture on 
impact or flexure. Cracks produced by impact or flexure often lead to 
chemical attack and deterioration, resulting in part from a wicking action 
at the damaged impact site. Various prior art attempts to produce 
polymeric materials having improved impact strength have generally 
resulted in a diminishing of corrosion resistance, thermal stability or 
other desirable property of the polymer. 
It is known that the presence of urethane linkages may contribute to the 
corrosion resistance of a polymer. Thus, for example, it is known to 
prepare corrosion resistant polymers from monomers having urethane 
linkages and ethylenically unsaturated terminal groups. U.S. Pat. No. 
3,297,745 discloses the preparation of such monomers by the reaction of 
one mole of a dihydric compound such as an alkylene, arylene or 
polyalkylene ether glycol, or a dihydric phenol such as a bisphenol, 
naphthalene diol, or the like with two moles of a diisocyanate to form a 
diisocyanate having two urethane linkages and subsequent reaction of the 
diurethane diisocyanate with two moles of an ethylenically unsaturated 
alcohol, such as an hydroxyalkyl acrylate. The resultant acrylate 
terminated tetraurethane monomer may polymerized or copolymerized with a 
vinyl monomer, such as styrene, to form corrosion-resistant polymers or 
copolymers. 
A wide variety of other polyurethane compositions are known and used 
commercially in the preparation of molded articles, laminates, coatings, 
films, adhesives, rigid and flexible foams and the like. The wide 
variation of polyurethane compositions and properties thereof stems from 
the ability of isocyanates to react with a variety of organic compounds 
having active hydrogen-containing groups. Among the many such compositions 
known in the art are polyurethanes prepared from polyisocyanates and 
various polyols, including for example polyether polyols, polyester 
polyols, polydienediols, novolacs, oxyalkylated novolacs, and others. 
In U.S. Pat. No. 3,278,293, for example, it is disclosed that improved 
physical properties and self-extinguishing characteristics may be obtained 
in polyurethane compositions derived from specific mixtures of polyether 
polyols, novolac resins and polyisocyanates. 
U.S. Pat. No. 3,497,465 discloses the preparation of polyurethanes 
especially useful in low temperature applications from the reaction of an 
organic polyisocyanate with a composition comprising an oxyalkylated 
phenol-aldehyde resin, a polyol prepared by reacting a polyhydric alcohol 
and a mono epoxide, a dihydric alcohol, such as ethylene glycol, an 
alkanolamine, and a phosphorus compound. 
U.S. Pat. No. 3,538,040 discloses the preparation of curing resins for 
foundry sands, by reacting an organic polyisocyanate with an oxyalkylated 
phenol-aldehyde or phenol-ketone condensate. U.S. Pat. No. 3,686,106 
discloses curable foundry binders of an oil modified hydroxyalkylated 
novolac resin, an unsaturated petroleum polymer, a solvent and an organic 
polyisocyanate. 
The foregoing prior art illustrates the wide variety of polyurethane 
compositions that may be prepared by reaction of a polyisocyanate and 
various polyols, including novolacs and oxyalkylated novolacs. It will be 
appreciated by those skilled in the art that despite the wide selection of 
known compositions and properties, a continuing need exists for new and 
better components and specific combinations of components for polyurethane 
compositions that will provide improved properties for various special 
applications, such as the manufacture of corrosion resistant articles and 
materials. 
It is an object of this invention to provide novel polyurethane 
compositions which may be copolymerized with an ethylenically unsaturated 
monomer. It is a further object to provide novel thermoset polyurethane 
compositions well suited for use in the manufacture of corrosion-resistant 
articles of manufacture. It is a still further object to provide polymeric 
materials and articles of manufacture having superior corrosion resistant 
properties as well as high impact strength. 
SUMMARY OF THE INVENTION 
It has now been found that thermoset polymer compositions having excellent 
corrosion resistance and impact strength are prepared from compositions 
comprising (A) an ethylenically unsaturated monomer and (B) a vinyl 
terminated polyurethane composition comprising the reaction product of an 
organic polyisocyanate, an hydroxyalkylated novolac, and an ethylenically 
unsaturated alcohol. 
the novel polymer compositions of this invention may be employed as 
coatings or fabricated by conventional techniques into various shapes or 
articles of manufacture such as reinforced laminates, castings, moldings 
and the like. Thus in one aspect the present invention relates to vinyl 
terminated polyurethane compositions and in a second aspect to thermoset 
polymer compositions prepared therefrom. In still another aspect, this 
invention relates to articles of manufacture or coatings prepared from 
such polymer compositions and to a method for the preparation thereof. 
In the preparation of the vinyl terminated polyurethane compositions of 
this invention an organic polyisocyanate is reacted on one side with the 
hydroxyl group of an ethylenically unsaturated alcohol, such as an 
hydroxyalkylacrylate, and on the other side with an hydroxyl group of an 
hydroxyalkylated novolac. 
The hydroxyalkylated novolacs useful in the preparation of the polyurethane 
compositions are those characterized by the formula: 
##STR1## 
wherein 
n has an average value of about 0.2 to 6, preferably about 0.5 to about 3; 
x, y and z are integers from 1 to 25, preferably about 1 to about 10; 
R.sub.1 is independently selected from the group consisting of hydrogen, 
fluorine, chlorine, bromine, a hydrocarbon radical, a halogen-substituted 
hydrocarbon radical, a hydrocarbon ketone radical and a hydrocarbon 
carboxylic radical; 
R.sub.2 and R.sub.3 are independently selected from the group consisting of 
hydrogen, a hydrocarbon radical, and a halogen-substituted hydrocarbon 
radical; and 
R.sub.4 is a hydrocarbon radical. 
Where R.sub.1, R.sub.2, R.sub.3 and/or R.sub.4 is a hydrocarbon or 
substituted hydrocarbon radical, the preferred hydrocarbon radicals are 
those containing up to about 12 carbon atoms. 
The preferred hydroxyalkylated novolacs are those characterized by the 
formula shown hereinabove wherein R.sub.1, R.sub.2 and R.sub.3 are 
hydrogen and R.sub.4 is a hydrocarbon radical containing 2 to 6 carbon 
atoms. 
The hydroxyalkylated novolac can be prepared by reacting (A) a fusible, 
organic solvent-soluble condensation product of a phenol and an aldehyde 
or ketone containing condensate units having reactive phenolic hydroxyl 
groups and (B) a substance reactive with the phenolic hydroxyl group and 
selected from the group consisting of a mono-oxirane ring compound, an 
alkylene halohydrin, and an alkylene carbonate and mixtures thereof. The 
hydroxylalkylated novolac can also be prepared by first reacting a phenol 
with the substance reactive with the phenolic hydroxyl groups, and 
thereafter condensing the modified phenol with an aldehyde or ketone. 
The fusible, organic solvent-soluble condensation products of a phenol and 
an aldehyde or ketone (novolacs) suitable for use in preparing the 
hydroxyalkylated novolacs of this invention are well known in the art and 
are described for example in U.S. Pat. No. 3,538,040, the disclosure of 
which is incorporated herein by reference. 
The hydroxyalkylated novolac condensation products preferably contain no 
free reactive phenolic groups, i.e., less than about 5%, but preferably 
less than about 0.5% of the phenolic hydroxyl present originally in the 
phenol-aldehyde or phenol-ketone condensate. 
The preferred method of hydroxyalkylation to produce the hydroxyalkylated 
novolacs useful in the invention is by reaction of the condensation 
products (novolacs) with compounds containing a mono-oxirane ring. 
Monomeric epoxides, such as ethylene oxide, propylene oxide, butylene 
oxide, cyclohexane oxide, or the like or mixtures thereof are preferred. 
Catalysts for the reaction of the oxirane ring compounds and phenolic 
hydroxyl groups are alkali or alkaline earth hydroxides, primary amines, 
secondary amines, tertiary amines or basic alkali salts such as sodium, 
potassium, and lithium hydroxides; amines such as methyl, dimethyl, 
diethyl, tripropyl, and the like; salts of strong bases and weak acids, 
such as sodium acetate or sodium benzoate. The hydroxyalkylation reactions 
can be carried out at 50.degree.-250.degree. C, but the hydroxyalkylation 
of phenols is preferably performed at 50.degree.-150.degree. C. The 
hydroxyalkylation of the phenolic condensates is preferably performed at 
150.degree. to 250.degree. C. 
The phenolic hydroxyl of the phenolic condensates can also be 
hydroxyalkylated by reacting it with alkylene halohydrins using equivalent 
amounts of an alkali metal hydroxide to bring about the reaction. Suitable 
alkylene halohydrins include, for example, ethylene chloro or 
bromohydrins, propylene chloro or bromohydrins, 2,3-butylene chloro or 
bromohydrins, glycerol chloro or bromohydrins or the like. Another method 
for hydroxyalkylating a phenolic novolac is by reaction with an alkylene 
carbonate; such as ethylene carbonate or propylene carbonate, using a 
catalyst such as sodium or potassium carbonate. 
Suitable organic polyisocyanates which may be employed in the preparation 
of the polyurethane compositions of this invention include a wide variety 
of aromatic, aliphatic and cycloaliphatic polyisocyanates. Typical 
polyisocyanates which may be employed include for example, 
4,4'-methylenebis (phenylisocyanate); 2,4-toluene diisocyanate; 
2,6-toluene diisocyanate; 1,5-naphthalene diisocyanate; tetramethylene 
diisocyanate; hexamethylene diisocyanate; pentamethylene diisocyanate; 
cyclohexyl-2,4-diisocyanate; 4,4'-methylenebis (cyclohexyl) diisocyanate; 
2,4,6-tolylene triisocyanate; 4,4',4"-triphenylmethane triisocyanate; 
polyaryl polyisocyanates; and the like, as well as mixtures of such 
isocyanates. The preferred organic polyisocyanates are the diisocyanates, 
typified, for example, by the formula OCNR.sub.5 NCO wherein R.sub.5 is an 
aryl, aliphatic or cycloaliphatic group. 
Ethlenically unsaturated alcohols which may be employed are those 
characterized by the formula 
##STR2## 
wherein R.sub.6 is --H, or --CH.sub.3 ; R.sub.7 is --H, --CH.sub.3, or 
--C.sub.6 H.sub.5 ; and A is a divalent organic radical selected from the 
group consisting of 
##STR3## 
wherein n is 3 to about 12, R.sub.8 is --H, --(CH.sub.2).sub.m --CH.sub.3, 
--CH.sub.2 CL, 
##STR4## 
CH.sub.2 OR.sub.9, or --CH.sub.2 OCH.sub.2 CH.dbd.CHR.sub.7 wherein m is 
an integer from zero to 10, and R.sub.9 is a phenyl or halogenated phenyl 
radical, alkyl or halogenated alkyl radical having from 2 to 4 carbon 
atoms, benzoxy or halogenated benzoxy radicals, phenoxy or halogenated 
phenoxy radical and R.sub.7 is as defined above. 
The preferred ethylenically unsaturated alcohols are hydroxyalkyl acrylates 
characterized by the formula 
##STR5## 
wherein R.sub.6 is --H or --CH.sub.3 ; and 
##STR6## 
wherein n is 3 to 12; and 
EQU R.sub.8 is --H or --(CH.sub.2).sub.m CH.sub.3 ; 
wherein m is zero to 10. 
Among the ethylenically unsaturated alcohols which may be employed are 
included, for example, allyl alcohol, 1-methyl allyl alcohol, 2-methyl 
allyl alcohol, allyl 2-hydroxyethyl ether, hydroxyalkyl acrylates and the 
like. The preferred ethylenically unsaturated alcohols are the 
hydroxyalkyl acrylates. The term "hydroxyalkyl acrylate" is employed in 
this specification and claims in a generic sense to include hydroxyalkyl 
acrylates as well as hydroxyalkyl methacrylates. Where reference is made 
to a specific compound of this type the appropriate species name -- 
acrylate or methacrylate -- is employed. Suitable hydroxy alkyl acrylates 
include, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl 
methacrylate, 2-hydroxy-1-methylethyl acrylate, 2-hydroxyl-1-methylethyl 
methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 
3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl 
acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 
4-hydroxybutyl methacrylate, 2-hydroxypentyl acrylate 2-hydroxypentyl 
methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate, 
2-hydroxyhexyl acrylate, 2-hydroxyhexyl methacrylate, 6-hydroxyhexyl 
acrylate, 6-hydroxyhexyl methacrylate, 2-hydroxyheptyl acrylate, 
2-hydroxyheptyl methacrylate, 7-hydroxyheptyl acrylate, 7-hydroxyheptyl 
methacrylate, 2-hydroxyoctyl acrylate, 2-hydroxyoctyl methacrylate, 
2-hydroxydodecenyl acrylate, 2-hydroxydodecenyl methacrylate, 
2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-chloropropyl methacrylate 
and the like as well as mixtures of these. The preferred hydroxyalkyl 
acrylates or methacrylates are those wherein the alkyl group is 2 to 4 
carbon atoms and most preferably hydroxypropyl methacrylate. 
The preparation of the urethane acrylates of this invention may be effected 
by first reacting the hydroxyalkylated novolac with an organic 
diisocyanate to form an isocyanate-terminated urethane, and subsequently 
reacting that intermediate isocyanate with an ethylenically unsaturated 
alcohol to form a vinyl terminated polyurethane, substantially free of 
unreacted isocyanate or hydroxyl groups. Alternatively, the three 
reactants, that is, the hydroxyalkylated novolac, diisocyanate and 
ethylenically unsaturated alcohol may be reacted together in a single 
step. In a preferred mode of preparation the ethylenically unsaturated 
alcohol is first reacted with the diisocyanate to form an isocyanate - 
terminated urethane, and subsequently that intermediate isocyanate is 
reacted with the hydroxyalkylated novolak. The reaction may be 
illustrated, in an idealized manner by the equation: 
##STR7## 
It will be appreciated that the foregoing equations and formulas represent 
idealized reactions and products and that various other side reactions may 
take place and other side products may be formed, normally in minor 
amounts. 
The proportions of the components of the polyurethane, that is the 
hydroxyalkylated novolac, ethylenically unsaturated alcohol, and 
polyisocyanate, may vary but are preferably in a range sufficient to 
provide a ratio of NCO:OH of about 0.75 to about 1.3 and most preferably 
about 1 to provide a substantially fully reacted polyurethane. The 
proportions of the hydroxyl-bearing reactants, that is the oxyalkylated 
novolac and the ethylenically unsaturated alcohol, necessary to provide 
the aforementioned ratio of NCO:OH may vary but is preferably in the range 
of about 0.75 to about 2.3 hydroxyl equivalents of hydroxyalkylated 
novolac per mole of ethylenically unsaturated alcohol. Most preferably the 
proportions are such as to provide about 0.75 to about 1.3 hydroxyl 
equivalents of hydroxyalkylated novolac and about 0.15 to 1.3 moles of 
ethylenically unsaturated alcohol per mole of diisocyanate. 
The urethane forming reaction proceeds readily at moderate temperatures, 
such as less than about 100.degree. Celsius, preferably about 10.degree. 
to about 90.degree. Celsius, without the aid of a catalyst. If desired, 
the reaction may be carried out in the presence of a conventional catalyst 
for isocyanate reactions such as tetramethylene guanidine, 
tetramethylenediamine, triethylenediamine, trimethylethylenediamine, 
dimethylethanolamine, trimethylamine, triethylamine, N-ethyl morpholine, 
N-ethyl piperidine, lead octoate, stannous oleate, stannous octoate, 
dibutyl tin dilaurate, stannic chloride, antimonous caprylate, antimony 
naphthenate, antimonous chloride, phenylmercuric acetate and the like as 
well as mixtures of such catalysts. 
The presence of moisture during the urethane forming reactions may result 
in the occurence of undesired isocyanate side-reactions, such as biuret 
formation. To avoid or minimize the occurence of such side-reactions, the 
reaction mixture should be substantially anhydrous, the moisture content 
of the reactants being preferably less than about 0.1 percent by weight. 
The urethane forming reactions may be carried out in the presence of a 
suitable inert solvent such as benzene, toluene or the like. Preferably, 
the reaction solvent is styrene, methyl methacrylate or other 
ethylenically unsaturated monomer which is also suitable for subsequent 
copolymerization with the hydroxyalkylated novolac urethane acrylate 
reaction product. The amount of reaction solvent employed may vary 
considerably as necessary to provide a suitable viscosity of the reaction 
mixture. When styrene or other ethylenically unsaturated monomer is 
employed as the reaction solvent it is preferred to incorporate in the 
reaction mixture, a suitable amount of a vinyl polymerization inhibitor to 
prevent premature polymerization of the unsaturated monomer. Suitable 
polymerization inhibitors such as catechol, hydroquinone, 
toluhydroquinone, benzoquinone, and the like may be employed, typically in 
amounts of about 0.001 to 1 weight percent of the reaction mixture. 
The vinyl terminated urethane composition thus prepared may be 
copolymerized with an ethylenically unsaturated monomer to produce a 
thermoset polymer composition characterized by excellent physical 
properties and a high degree of resistance to acids and alkalies. Suitable 
ethylenically unsaturated monomers which may be employed in the 
preparation of the thermoset polymer include, for example, styrene, 
chlorostyrenes, methyl styrenes, vinyl benzyl chloride, divinylbenzene, 
vinyl toluene, fluorostyrene, unsaturated esters such as methyl acrylate, 
methyl methacrylate, as well as lower aliphatic esters of acrylic or 
methacrylic acids, and the like as well as mixtures of such unsaturated 
monomers. The ethylenically unsaturated alcohol can act as the unsaturated 
monomer if reacted in stoichiometric excess in generating the urethane 
acrylate. Furthermore, an excess of the unsaturated alcohol may be 
employed for this purpose in admixture with other unsaturated monomers. 
The proportion of unsaturated monomer to vinyl terminated urethane may vary 
within the ultimate limits of each as necessary to produce an infusible 
thermoset resin. Generally the weight proportion of unsaturated monomer is 
about 0.5 to about 2.0, and preferably about 0.75 to about 1.3 part of 
unsaturated monomer per part of vinyl terminated urethane product. 
Polymerization catalysts are preferably added to the mixture of unsaturated 
monomer and vinyl terminated urethane to effect setting or curing. 
Catalysts of the free radical type such as benzoyl peroxide, acetyl 
peroxide, lauroyl peroxide, methylethyl ketone peroxide, cumene 
hydroperoxide and the like may be employed, typically in proportion of 
about 0.01 to about 10 weight percent of the reaction mixture depending on 
the efficiency of their action and whether or not a polymerization 
inhibitor is present in the reaction mixture. Furthermore, various known 
polymerization promotors such as dimethylaniline or the like may be 
employed, typically in amounts equal to or less than the amount of 
catalyst employed. The polymerizable composition, thus prepared, may be 
applied as a coating or molded or cast in a known manner. Typically, the 
resultant thermoset composition may be cured at ambient conditions for up 
to about 24 hours and post cured at an elevated temperature, such as about 
100.degree. C for a shorter period such as one to two hours. 
In an alternative embodiment of this invention, it has been found that 
still further improvement in flexibility and impact strength may be 
achieved by incorporation of a minor proportion of an hydroxyalkylated 
polyol in the hydroxyalkylated novolac reactant. The hydroxyalkylated 
polyol may be prepared by reaction of a polyol with a compound containing 
a mono-oxirane ring such as ethylene oxide, propylene oxide, butylene 
oxide, cyclohexane oxide or the like or mixtures of such compounds. The 
resultant hydroxyalkylated polyol may be added to the hydroxyalkylated 
novolac and/or directly to the reaction mixture containing the 
aforementioned isocyanate reactant. Preferably the hydroxyalkylated polyol 
is formed in situ during the preparation of the hydroxyalkylated novolac 
by addition of the polyol to the novolac composition prior to the 
hydroxyalkylation step. Preferred polyols which may be employed for this 
purpose are low molecular weight polyols having up to about 6 carbon 
atoms, and include, for example, glycerine, pentaerythritol, trimethylol 
ethane, and trimethylol propane, glycols such as propylene glycol, and the 
like, as well as mixtures of such polyols. The amount of polyol 
incorporated in the novolac composition may vary considerably but is 
preferably in the range of about 5 to 75 parts by weight and most 
preferably about 40 to 60 parts by weight per 100 parts of novolac. 
The vinyl-terminated urethane compositions of this invention may be 
employed as coating compositions, either alone or in admixture with 
conventional coating formulation additives such as solvents, fillers, 
pigments and the like. Furthermore they may be combined with a reactive 
solvent, such as styrene or other copolymerizable ethylenically 
unsaturated monomers such as those described hereinabove to form coating 
compositions of the type known as 100 percent solids coating compositions. 
The coating compositions may be applied by conventional means, such as 
brushing, spraying, dipping, rolling, and the like to form a durable 
corrosion resistant coating. The salt water resistance of these coatings 
makes them well suited for use as marine finishes. The coatings may be 
cured by known means, such as exposure to heat, light, electron radiation 
x-ray radiation, or with the aid of known peroxide catalysts and 
promotors. 
It is to be understood that fillers, dyes, pigments, lubricants, solvents, 
fire retardants, and various other adjuvants and modifying agents may be 
incorporated in the compositions of this invention in order to obtain or 
accentuate any given property. Furthermore moldings and laminates may be 
prepared by the addition of suitable reinforcing agents such as glass 
rovings, glass mat, asbestos fiber and the like.

The following specific examples are provided to further illustrate this 
invention and the manner in which it may be carried out. It will be 
understood that the specific details given in the examples have been 
chosen for purposes of illustration and are not to be construed as a 
limitation on the invention. In this specification and claims, unless 
otherwise indicated, all parts and percentages are by weight and all 
temperatures are in degrees Celsius. 
EXAMPLES 1-6 -- PREATION OF THE HYDROXYALKYLATED NOVOLAC RESIN 
EXAMPLE I 
A mixture of 1880 parts of phenol, 303 parts of paraformaldehyde, and 9.5 
parts of maleic anhydride catalyst was heated to reflux temperatures of 
102.degree. to 105.degree. C and maintained thereat for one hour. The 
reaction product was dehydrated and dephenolated by heating to a final 
temperature of 210.degree. C at 70mm Hg. The product was 1373 parts of a 
novolac resin characterized by 1.425 ArOH per methylene bridge. Then 0.7 
parts of potassium hydroxide (0.05% by weight, based on novolac weight) 
was added and propylene oxide was added at a temperature of about 
165.degree.-195.degree. C until a weight increase of 855 parts was 
attained. The resultant condensation product had an hydroxyl number of 336 
and a calculated proportion of 1.1 mole of propylene oxide per mole of 
phenolic hydroxyl in the novolac. 
EXAMPLE 2 
An hydroxyalkylated novolac was prepared as follows: 3000 parts of phenol, 
13 parts of maleic anhydride catalyst and 6 parts of an alkylaryl 
sulfonate type of wetting agent were introduced into a jacketed reactor 
and heated to about 100.degree. C. Then 847 parts of a 49% aqueous 
formaldehyde solution was added at such a rate that the heat of reaction 
provided a vigorous reflux. Refluxing was continued for an additional 
hour. The reaction product was dehydrated at 180.degree. C and then 
dephenolated to 220.degree. C at a pressure of 50 mm Hg. Approximately 
2070 parts of phenol-aldehyde condensate was produced. Four parts of 
potassium hydroxide was introduced to the reactor. The reactor temperature 
was maintained at about 165.degree. to 195.degree. C while 1383 parts of 
propylene oxide was added thereto. The resultant condensation product had 
an hydroxyl number of 322. 
EXAMPLE 3 
An hydroxyalkylated phenol-aldehyde novolac was prepared following the 
procedure of Example 2 except that a total of 1692 parts of propylene 
oxide was added. 
EXAMPLE 4 
An hydroxyalkylated phenol-aldehyde novolac was prepared as in Example 2 
until the addition of 2100 parts of propylene oxide was complete. 
EXAMPLE 5 
An hydroxyalkylated phenol-aldehyde novolac was prepared by introducing 
13,080 parts phenol, 52 parts of maleic anhydride catalyst and 26 parts of 
a wetting agent into a jacketed reactor and heating to 100.degree. C. Then 
4840 parts of a 45% aqueous formaldehyde solution were added and reacted 
as in Example 2. The reaction was dehydrated and dephenolated as in 
Example 2 to yield 10,000 parts of novolac. Potassium hydroxide, 0.2% by 
weight on the novolac condensate, was added and propylene oxide was added 
at 165.degree. to 195.degree. C until 1.45 propylene oxide had reactor per 
phenolic hydroxyl. 
EXAMPLE 6 
A glycerin-modified hydroxyalkylated phenol-aldehyde novolac composition 
was prepared by introducing 522 parts phenol, 2 parts of maleic anhydride 
catalyst and 1 part of a wetting agent into a jacketed reactor and heating 
to 100.degree. C. Then, 113 parts of a 45% aqueous formaldehyde solution 
were added and reacted as in Example 2. The reaction was dehydrated and 
dephenolated as in Example 2 to yield 261 parts of phenol-aldehyde novolac 
condensate. To this was added 125 parts of glycerine and 1.5 parts of 
potassium hydroxide. Propylene oxide was then added to the reactor until 
the addition of 296 parts was complete. Ethylene oxide was then added to 
the reactor until the addition of 313 parts of complete. 
The characteristics of the hydroxyalkylated novolacs prepared according to 
Examples 1-6 are set forth in Table I, below. 
TABLE I 
______________________________________ 
Ratio of 
Phenol 
to Aldehyde 
Novolac Ratio of Hy- 
Ex. in Base Function- 
Alkylene Oxide 
droxyl 
No. Condensate ality to Hydroxyl Group 
No. 
______________________________________ 
1 3/2 to 4/3 3.5 1.1 propylene oxide 
336 
2 3/2 3. 1.17 propylene oxide 
322 
3 3/2 3. 1.45 propylene oxide 
293 
4 3/2 3. 1.85 propylene oxide 
255 
5 4/3 3.7 1.45 propylene oxide 
285 
6 2/1 to 3/2 2.7 0.8 propylene oxide & 
355 
1.1 ethylene oxide 
______________________________________ 
EXAMPLES 7-12-- PREATION OF VINYL-TERMINATED POLYURETHANES 
The following examples illustrate the preparation of the vinyl-terminated 
polyurethane compositions of this invention. 
EXAMPLE 7 
A vinyl terminated, fully reacted urethane acrylate was prepared by 
charging 422 parts of the oxypropylated novolac prepared in Example 1 
(2.65 hydroxyl equivalents), 381 parts of hydroxypropyl methacrylate (2.65 
moles), 1283 parts of styrene solvent, and 0.28 parts of p-benzoquinone 
inhibitor to a reactor and heating to 50.degree. C to effect dissolution 
of the reactants. To the solution was added 460 parts (2.65 moles) of 
toluene diisocyanate (a commercially available mixture of approximately 80 
percent 2,4-isomer and 20 percent 2,6-isomer) and the solution was heated 
and maintained at about 70.degree. - 80.degree. C with stirring for about 
4 hours. 
EXAMPLES 8-12 
A series of fully reacted urethane acrylates were prepared by reacting one 
hydroxyl equivalent of the hydroxyalkylated novolacs of Examples 2 through 
6 and one mole of hydroxypropylmethacrylate with one mole of toluene 
dissocyanate following the procedure of Example 7. The properties of the 
polyurethane acrylates thus prepared are set forth in Table II, below. 
TABLE II 
______________________________________ 
Hydroxy- 
alkylated 
Polyurethane 
Novolac Brookfield 
Acrylate Ex. No. Visc. at 25.degree. C 
Example From at 100 (phr) 
Gardner 
Number Table I styrene H Color % NCO 
______________________________________ 
7 1 336 3 -- 
8 2 300 6 0.58 
9 3 650 7 0.42 
10 4 300 6 0.43 
11 5 600 7 -- 
12 6 300 10 0.36 
______________________________________ 
EXAMPLE 13 
A 1/8 inch casting was made from the prepared polyurethane acrylate 
composition of Example 7. The casing was cured using 2% of a paste 
containing 50% benzoyl peroxide in tricresyl phosphate as catalyst with 
0.125% dimethyl aniline as promoter. The casting was allowed to cure at 
room temperature for 24 hours and was then post cured at 110.degree. C for 
one hour. The properties of the casting were: 
______________________________________ 
Flexural Strength, psi 14,200 
Flexural Modulus 4.3 .times. 10.sup.5 
Tensile Strength, psi 7,300 
% Elongation at Break 1.47 
______________________________________ 
EXAMPLE 14 
A 1/8 inch laminate was prepared from 3 -- plies of 2 ounce glass mat using 
the above prepared composition of Example 7 as a binder therefore. The 
laminate was cured using 2% of a paste containing 50% benzoyl peroxide in 
tri cresyl phosphate as catalyst with 0.125% dimethylaniline promoter. The 
laminate was allowed to cure for 24 hours at room temperature and then 
post-cured at 110.degree. C for 2 hours. The properties of the laminate 
were: 
______________________________________ 
Flexural Strength, psi 
24,400 
Tensile Strength, psi 16,900 
Modulus Flexure 9.12 .times. 10.sup.5 
Barcol Hardness 55 
% Glass in Laminate 30 
______________________________________ 
EXAMPLE 15 
A 1/8 laminate was prepared from two plies veil, 2 plies of 1-1/2 ounce 
glass mat using the above prepared composition of Example 7 as a binder 
therefore. The laminate was cured using 2% of a paste containing 50% 
benzoyl peroxide in tri cresyl phosphate as catalyst with 0.125% dimethyl 
aniline as promoter. The laminate was allowed to cure at room temperature 
for 24 hours and then post-cured at 110.degree. C for 2 hours. 
The corrosion resistance of the polymer; i.e. the resistance to attack by 
chemical reagents, was demonstrated by immersing samples of the laminate 
prepared above in various reagents for 96 hours under reflux conditions, 
and measuring the weight loss occasioned by this treatment. The results of 
this test follow: 
______________________________________ 
Reagent % Weight Change 
______________________________________ 
1/2% NaOH 1.03 
10% NaOH 2.43 
10% H.sub.2 SO.sub.4 
1.02 
Distilled H.sub.2 O 
0.93 
______________________________________ 
The samples in 1/2% NaOH, 10% H.sub.2 SO.sub.4 and distilled water were not 
substantially changed. The samples in 10% NaOH showed slight 
deterioration. These results clearly indicate the excellent corrosion 
resistance of the styrenated polymer of this example. Glass mat laminates 
made with the new resin undergo some attack in caustic even though the 
resin itself is resistant to strong alkali. This is because glass fibers 
near the surface can become exposed and permit wicking of the corrosive 
solution into the body of the laminate. Laminates made from polypropylene 
cloth were inert to caustic. 
The impact resistance of the prepared polyurethane acrylate compositions 
was demonstrated in the following manner using a dropping ball test as 
described in ASTM D-2444. Laminates were prepared as in Example 15 from 
the polyurethane acrylate compositions. A 1/2 lb. ball was dropped from a 
height of 14 inches on to the laminate. The average diameter of the 
shatter area is reported in inches. The test was repeated from a drop 
height of 30 inches. 
______________________________________ 
Average Diameter 
of Shatter 
Polyurethane Acrylate Composition 
Area, Inches 
From Table II 14 Inch Drop 
30 Inch Drop 
______________________________________ 
8 0.4 1.2 
9 0 0.9 
10 0 1.1 
12 0 0.5 
Bisphenol-A Fumarate (BPA) 
1 2 
Flexibilized BPA Fumarate 
0.9 1.25 
______________________________________ 
The table includes a commercially available BPA fumarate and flexibilized 
version (having additional oxypropylation) for comparison. Both BPA 
fumarate types are commonly used in the chemical resistant field. The 
polyurethane acrylate compositions are seen to give much better impact 
resistance. Furthermore, it will be noted that still additional advantage 
in impact strength is achieved in the composition of Example 12, prepared 
from the glycerin-modified oxyalkylated novolac of Example 6. 
To demonstrate the further improvements in impact strength achieved through 
the incorporation of an hydroxyalkylated polyol in the compositions of 
this invention, a series of compositions were prepared with and without a 
polyol modifier and tested for impact strength. The preparation and 
testing of the compositions is described in the following examples. 
EXAMPLE 16 
A glycerin-modified oxypropylated novolac was prepared as follows: 
A. A mixture of 455 parts of phenol, 1.7 parts of maleic anhydride 
catalyst, and 1 part of an alkylaryl sulfonate type of wetting agent was 
introduced into a jacketed reactor and heated to about 100.degree. C. Then 
91.5 parts of a 48.5 percent aqueous formaldehyde solution was added at a 
rate such that the heat of reaction provided a vigorous reflux. Refluxing 
was continued for an additional hour. The reaction mixture was dehydrated 
at 180.degree. C and then dephenolated to 225.degree. C at a pressure of 
50 millimeters of mercury. 
B. Then 113 parts of glycerine and 1.4 parts of potassium hydroxide was 
introduced to the reactor. The reaction temperature was maintained at 
about 165.degree. to 195.degree. C while 644 parts of propylene oxide was 
added thereto. The reaction mixture was cooled to 180.degree. C and 3.1 
parts of butyl acid phosphate was added and mixed while the temperature 
was maintained at about 180.degree. C for about one hour. The resulting 
condensation product had an hydroxyl number of 328. 
EXAMPLE 17 
A vinyl terminated, fully reacted urethane acrylate was prepared from the 
glycerine-modified hydroxyalkylated novolac of Example 16 in the following 
manner: A mixture of 1155 parts of styrene solvent, 415 parts of 
hydroxypropyl methacrylate, and 0.4 parts of p-benzoquinone was stirred 
while 519 parts of toluene diisocyanate (a mixture of approximately 80 
percent 2,4-isomer and 20 percent 2,6-isomer) was added slowly so that the 
temperature did not exceed 45.degree. C. The temperature was then raised 
to 55.degree. C and maintained thereat for about 30 minutes. Then 510 
parts of glycerine-modified hydroxypropylated novolac, prepared as in 
Example 16 was added and the reaction mixture was heated to 65.degree. C 
an maintained at that temperature for about 4 hours. The liquid resin, 
thus prepared had a Brookfield viscosity of 120 centipoises at 25.degree. 
C. 
EXAMPLE 18 
Following the procedure of Example 15, a laminate was prepared from the 
vinyl terminated urethane acrylate of Example 17. Impact resistance of the 
laminate was measured using the above-described falling ball test. A one 
half pound ball dropped from 30 inches (1.25 ft-lbs) yielded a shatter 
area measuring 0.2 inches in diameter. A one pound ball dropped from 30 
inches (2.5 ft-lbs) yielded a shatter area 0.4 inches in diameter. 
EXAMPLE 19 
A propylene glycol-modified hydroxyalkylated novolac was prepared in the 
following manner. A phenolic novolac was prepared as described in Example 
16 A. To 404 parts of this phenolic novolac were added 193 parts of 
propylene glycol and 2.3 parts of potassium hydroxide. Then propylene 
oxide was added in the manner described in example 16 B until a total of 
1030 parts of propylene oxide had reacted. The resultant condensation 
product had an hydroxyl number of 275. 
EXAMPLE 20 
An hydroxyalkylated novolac without a glycol modifier was prepared 
following the procedure of Example 19 except that: no propylene glycol was 
added; potassium hydroxide was added in the amount of 1.6 parts; and 
propylene oxide was added until a total amount of 425 parts had reacted. 
The resultant condensation product had an hydroxyl number of 259. 
EXAMPLES 21-25 
A series of vinyl-terminated urethane acrylates in styrene were prepared 
following the procedure of Example 17 except that the composition was 
varied as shown in the table below: 
__________________________________________________________________________ 
Example Number 
Composition (in parts by weight) 
17 21 22 23 24 25 
__________________________________________________________________________ 
Condensation product of Ex. 16 
510 521 -- -- -- -- 
Condensation product of Ex. 19 
-- -- 570 581 -- -- 
Condensation product of Ex. 20 
-- -- -- -- 591 603 
Hydroxypropyl methacrylate 
415 -- 388 -- 379 -- 
Hydroxypropyl acrylate 
-- 393 -- 367 -- 358 
Toluene diisocyanate 
519 530 486 496 474 483 
Styrene 1155 
1155 
1156 
1156 
1155 
1155 
p-Benzoquinone 0.4 0.4 0.4 0.4 0.4 0.4 
__________________________________________________________________________ 
Following the procedure of Example 15, laminates were prepared using the 
vinyl terminated urethane acrylate compositions of Examples 17 and 21-25. 
The impact resistance of the laminates was determined as in Examples 15 
and 18, using the falling ball test, with the following results: 
______________________________________ 
Laminate Prepared 
Shatter Area Diameter (inches) 
from: 1.25 ft.-lbs 2.5 ft-lbs 
______________________________________ 
Ex. 17.sup.(1) 
0.2 0.4 
Ex. 21.sup.(1) 
0.2 0.3 
Ex. 22.sup.(2) 
0 0.5 
Ex. 23.sup.(2) 
0.4 0.9 
Ex. 24.sup.(3) 
0.4 1.0 
Ex. 25.sup.(3) 
0.6 1.2 
______________________________________ 
.sup.(1) glycerin-modified compositions 
.sup.(2) propylene glycol-modified compositions 
.sup.(3) no glycol modifier