Novel dipropargyl ether of alpha, alpha'-bis(4-hydroxyphenyl)-para-diisopropylbenzene is useful in preparing resins having desirable properties as laminates and the like.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to the dipropargyl ether of alpha, 
alpha'-bis(4-hydroxyphenyl)-para-diisopropylbenzene and its use in resins, 
laminates and the like. 
2. State of the Art 
U.S. Pat. Nos. 4,226,800, 3,300,456, and 3,594,175; British patent No. 
1,149,697; and Hay et al. Polymer Letters, Part B, Vol. 8, No. 2, 97-99 
1970 describe various acetylene-terminated compounds, including the 
bispropargyl ether of bisphenol A. However, polymer resins prepared from 
this compound are undesirable for preparing electrical laminates because 
the resulting solutions thereof too readily run off reinforcing materials, 
such as fiberglass, and it is difficult to control the polymerization of 
the compound to provide a desired certain and reliable viscosity. 
SUMMARY OF THE INVENTION 
The present invention is directed to novel dipropargyl ether of alpha, 
alpha'-bis(4-hydroxyphenyl)-para-diisopropylbenzene of Formula I: 
##STR1## 
The compound, also known as dipropargyl ether of bishydroxycumylbenzene 
(DPE-BHCB), is useful in the preparation of polymers, including those 
having a high glass transition temperature (Tg) desirable in electrical 
laminates. The polymers also have a low dielectric constant, low moisture 
adsorption and more hydrocarbon in the polymer backbone. This result in 
the production of laminates with less run-off from the substrate and the 
laminates have a low dissipation factor useful in electrical applications. 
The novel dipropargyl ether monomer of the invention can be prepared by 
known methods including reacting the corresponding di-hydric phenolic 
material, alpha, alpha'-bis(4-hydroxyphenyl)-paradiisopropylbenzene, with 
a propargyl halide, such as chloride or bromide, in an aqueous alkaline 
solution, such as aqueous sodium hydroxide solution as described in U.S. 
Pat. No. 4,226,800, the disclosures of which are incorporated by 
reference. One preferred method is by using propargyl chloride in an 
aqueous sodium hydroxide and a water-miscible, protic co-solvent, which is 
disclosed and claimed concurrently filed U.S. patent application Ser. No. 
271,133, filed Nov. 14, 1988 now abandoned, the disclosures of which are 
incorporated by reference. 
The novel dipropargyl ether monomer of the invention can be used to make 
various polymers and curable resins. The most common kind of polymer can 
be prepared by oxidative coupling according to known methods, including 
Hay et al., Polymer Letters, 8, pp. 97-99 (1970). Another kind of polymer 
can be prepared by thermal polymerization to give thermoset polymers that 
are crosslinked. 
For electrical and electronic applications, a resin having a decomposition 
temperature higher than about 300.degree. C. is desirable. By addition 
polymerization of the novel dipropargyl ether of Formula I of the 
invention, polymers are obtained which have (a) a sharp melting point and 
(b) dependable viscosity when used in solutions. For example, when 
preparing an electrical laminate on, e.g., fiberglass, using a solution of 
the dipropargyl ether of Formula I of the invention in a solvent, such as 
a blend of toluene, dimethyl formamide/acetone, the resulting polymer has 
a high, dependable viscosity after the solvent has been dried off and the 
polymer will coat the fiberglass much better with less run-off than the 
corresponding polymer of the dipropargyl ether of bisphenol A. 
While not being limited to any theory, it is believed that the polymers 
have the Formula II 
##STR2## 
The catalysts which can be used in the present invention are conventional 
addition polymerization catalysts known in the art. Suitable catalysts 
include Group VI and Group VIII metal complex catalysts. Preferably, the 
addition polymerization catalyst is a nickel, platinum or palladium 
complex, such as molybdenum carbonyl, nickel acetylacetonate, 
tetrakis(triphenylphosphine)palladium 0, 
bis(1,3-diphenyl(phosphino))ethane nickel II chloride, 
bis(triphenylphosphine)palladium II chloride and the like. 
Another embodiment of the invention is directed to a method of preparing 
propargyl aromatic ether thermosetting polymers which comprises treating a 
propargyl aromatic ether with an effective amount of an addition 
polymerization catalyst. 
Another embodiment of the invention is directed to a laminate comprising a 
thermosetting polymer of a propargyl aromatic ether prepared by 
polymerization of a propargyl aromatic ether in the presence of an 
effective amount of the polymerization catalyst and a fibrous filler or 
reinforcing material. 
The curable composition of this invention can each be used in any desired 
form such as solid, solution or dispersion. These components are mixed in 
solvent or in the absence of a solvent to form the compositions of this 
invention. For example, the mixing procedure comprises mixing solutions of 
the composition in a suitable inert organic solvent or solvent blend, such 
as, for example, ketones such as acetone or methyl ethyl ketone, aprotic 
polar solvents, such as dimethyl formamide, aromatic hydrocarbons such as 
toluene, chlorinated hydrocarbons such as methylene chloride, ethers and 
the like, and homogenizing the resulting mixed solution at room 
temperature or at an elevated temperature below the boiling point of the 
solvents to form a composition in the form of a solution. When 
homogenizing these solutions at room temperature or at an elevated 
temperature, some reactions may take place between the constituent 
elements. So long as the resins components are maintained in the state of 
solution without gelation, such reactions do not particularly affect the 
operability of the resulting composition in, for example, a bonding, 
coating, laminating or molding operation. 
The curable resin compositions of invention can be used in the above 
solution form as adhesives, paint vehicles, molding materials to be 
impregnated in substrates, or laminating materials. In this case, the 
concentration of the resin solid in the solution is determined so that the 
optimum operability can be obtained according to the desired utility. 
The resin compositions of this invention can be used for various purposes 
in the form of dried powder, pellets, resin-impregnated product or 
compound. For example, compositions with the individual components 
uniformly mixed can be obtained by uniformly mixing the resin components 
in solution, and then removing the solvents from the homogeneous solution 
at reduced pressure or at an elevated temperature. Alternatively, solids 
components are kneaded at room temperature or at an elevated temperature 
to form a homogenized resin composition. The resin compositions can also 
melt blend and melt impregnate. 
The curable composition of this invention may be reticulated by heating it 
alone to form a cured resin having heat resistance. In general, a catalyst 
may be used in order to promote crosslinking reaction of the components in 
the composition. 
Examples of the catalysts include imidazoles, such as 2-methylimidazole, 
2-undecylimidazole, 2-heptadecylimidazole, 2phenylimidazole, 
2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 
1-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 
1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 
1-cyanoethyl-2-phenylimidazole, 1-guanaminoethyl-2-methylimidazole and 
addition product of an imidazole and trimellitic acid; tertiary amines, 
such as N,N-dimethyl benzylamine, N,N-dimethylaniline, 
N,N-dimethyltoluidine, N,N-dimethyl-p-anisidine, 
p-halogeno-N,N-dimethyl-aniline, 2-N-ethylanilino ethanol, 
tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, 
triethanolamine, triethylenediamine, N,N,N',N'-tetramethylbutanediamine, 
N-methylpiperidine; phenols, such as phenol, cresol, xylenol, resorcinol, 
and phloroglucin., organic metal complexes or salts, such as copper 
tetrafluoroborate, lead naphthenate, lead stearate, zinc naphthenate, zinc 
octoate, tin oleate, dibutyl tin maleate, manganese naphthenate, cobalt 
naphthenate, and acetyl acetone nickel or iron, 
bis(triphenylphosphine)palladium II dichloride, 
tetrakis(triphenylphosphine)palladium 0, bis(1,2-diphenylphosphino)ethane 
nickel II chloride, and inorganic metal complexes and salts, such as 
stannic chloride, zinc chloride and aluminum chloride; peroxides, such as 
benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, acetyl peroxide, 
para-chloro-benzoyl peroxide and di-t-butyl diperphthalate; acid 
anhydrides, such as maleic anhydride, phthalic anhydride, fumaric 
anhydride, pyro-mellitic anhydride, trimellitic anhydride, 
hexahydrophthalic anhydride, hexahydropyromellitic anhydride and 
hexahydrotrimellitic anhydride; azo compounds, such as 
azoisobutylonitrile, 2,2'-azobispropane, m,m'-azoxystyrene, hydrozones, 
and mixtures thereof. The amount of catalyst varies considerably according 
to the type of catalyst, the utility or curing conditions. They can, 
however, be used in catalytic amounts such as, for example, less than 5% 
by weight of the total composition. Bis(triphenylphosphine)palladium (II) 
dichloride is preferred. 
A variety of additives may be added to the curable composition to impart 
specific properties provided that they do not impair the essential 
properties of the resulting resin. Examples of the additives include 
natural or synthetic resins, fibrous reinforcement, fillers, pigments, 
dyestuffs, thickening agents, wetting agents, lubricants, flame-retardants 
and the like. 
The resin composition of this invention can also contain a white pigment 
such a titanium dioxide, a colored pigment such as yellow lead, carbon 
black, iron black, molybdenum red, prussian blue, ultramarine, cadmium 
yellow or cadmium red, and other various organic dyes and pigments in 
order to color the compositions. In addition to the above colored 
pigments, the resin compositions can also contain a rust-proofing pigment 
such as zinc chromate, red lead, red iron oxide, zinc flower or strontium 
chromate, an anti-sag agent such as aluminum stearate, a dispersing agent, 
a thickener, a coat modifier, a body pigment or a fire retardant, which 
are known additives for paints. 
The compositions of this invention are cured by heating after applying it 
to a substrate as a coating or adhesive layer, or after molding or 
laminating in the form of powder, pellet or as impregnated in a substrate. 
The curing conditions of the curable composition of this invention depend 
on the proportion of components constituting the composition and the 
nature of the components employed. In general, the composition of this 
invention may be cured by heating it at temperature within the range of 
about 0.degree.-300.degree. C., preferably about 100.degree. 
C.-250.degree. C., although differing according to the presence of a 
catalyst or curing agent or its amount, or the types of the components in 
the composition. The time required for heating is generally 30 seconds to 
10 hours, although considerably differing according to whether the resin 
composition is used as a thin coating or as molded articles of relatively 
large thickness or as laminates or as matrix resins for fiber reinforced 
composites, particularly for electrical and electronic applications, e.g., 
when applied to an electrically conductive material, such as copper, and 
subsequently cured. Suitable fibrous reinforcing materials include glass 
fibers, quartz fibers, carbon fibers, boron fibers, Kevlar.RTM. fibers, 
Teflon.RTM. fibers and the like with woven or continuous glass fibers or 
carbon fibers being preferred. The fibrous or reinforcing material is 
present in the compositions of the invention in an amount effective to 
impart increased strength to the composition for the intended purpose, 
generally about 20 to about 95 w percent, usually about 35 to about 85 w 
percent, based on the weight of the total composition. When the resin 
composition of this invention is used for producing molded articles, 
laminated articles or bonded structures, the curing is desirably effected 
under pressure. Generally, this pressure is from 5 to 100 Kg/cm.sup.2 
(gauge). 
The composition of this invention cures rapidly, even under mild 
conditions, so is especially suitable when quantity production and ease of 
workability are desired. The cured resin made from the composition not 
only has excellent adhesive force, bond strength, heat resistance, and 
electric properties, but also is excellent in mechanical properties and 
resistance to impact, chemicals, moisture and the like. The composition of 
this invention has a variety of uses as a coating material for rust 
prevention, flame resistance, flame retardance and the like., as 
electrical insulating varnish; as adhesive, in laminates to be used for 
furnitures, building materials, sheathing materials, electrical insulating 
materials, and the like; and in a variety of moldings.

ILLUSTRATIVE EMBODIMENTS 
The present invention is further illustrated by the following embodiments 
which should not be regarded as limiting the invention in any way. 
Embodiment I 
The dipropargyl ether of bishydroxycumylbenzene (BCHB) was prepared by 
treating 200 g of BCHB with 168 g of propargyl chloride added over about 
1/2 hour at 135.degree. F. in the presence of (a) sodium hydroxide in a 
molar ratio sodium hydroxide to phenol of 1.25 and (b) a reaction medium 
comprising 669 g of isopropyl alcohol (IPA) and 2050 g of water at 
150.degree.-155.degree. F. The reaction was continued for about 25 hours 
while maintaining the pH.gtoreq.11. The reaction product was cooled to 
room temperature, where the product crystallized out of solution. This 
product was washed twice with IPA and then with water until a constant pH 
of wash water was obtained. The product crystals were then blown dry to 
obtain the desired product in 67% yield (179.8 g). Product was then 
recrystallized, by dissolving into boiling IPA, filtering to remove any 
residues and allowing to cool to room temperature. The filtrate, now 
cloudy and containing precipitate, was further cooled to 0.degree. C. 
overnight. Then, the cold mixture was filtered, the solids washed with 
IPA, and dried in a vacuum oven overnight, at room temperature. A vacuum 
of 25 in Hg was maintained by bleeding nitrogen into the oven. Final 
realized yield was 58.7 % W, or 157.4 grams. 
Embodiment 2 
Prepregs were prepared from DPE-BHCB resin compositions as follows: 
TABLE 1 
______________________________________ 
Dipropargyl Ether Prepreg Manufacture 
from Solvent Borne Resin Varnish 
Property Value 
______________________________________ 
Resin DPE-BHCB 
Varnish 
Formulation, % w 
DPE-BHCB 49.9 
Dimethyl formamide 17.3 
Toluene 16.4 
Acetone 16.4 
Bis(triphenylphosphine)- 
palladiumdichloride phr (ppm Pd) 
.40(600) 
Gel Time, Seconds @ 171.degree. C. 
245 
Prepreg 
Glass Style 7628 
Processing Conditions 4.0 
Oven Time, Minutes 4.0 
Oven Temperature, .degree.C. 
163 
Resin Content, % w 28 
______________________________________ 
Embodiment 3 
Prepregs and laminates were prepared from DEP-BHCB resin compositions as 
follows: 
TABLE 3 
______________________________________ 
Dipropargyl Ether Prepreg and Laminate Preparation 
Using Resin Melt Coating Impregnation 
Property Value 
______________________________________ 
Resin DPE-BHCB 
Coating Mixture 
Formulation, % w 
DPE-BHCB 100 
Bis(triphenylphosphine)- 
0.40(600) 
palladiumdichloride ph (ppm PD) 
Gel Time, Seconds @ 171.degree. C. 
340 
Prepreg 
Glass Style 7628 
Processing Conditions 
Impregnation Time, Minutes 
2.5-3.0 
Impregnation Temperature, .degree.C. 
171 
Resin Content, % w 41.3 
Lamination 
Laminate Construction 
Size, in .times. in. 4 .times. 4 
Number of Plies 8 
Actual Processing Conditions 
Heat-up Rate, .degree.F./Minute (avg.) 
9 
Cure Schedule: 
Temperature, .degree.F./Time, Hours 
Hold 1 (cure) 600/1.5 
Hold 2 (postcure) 400/1.7 
Hold 3 (postcure) 440/1.5 
Hold 4 (postcure) 480/0.5 
Pressure, psi 
During Heat-up, Start-End 
5-150 
During Cure 150 
______________________________________ 
The properties of the resulting laminates are set forth in Table 4 as 
compared to a standard brominated epoxy resin laminate. 
TABLE 4 
______________________________________ 
Dipropargyl Ether Laminate Properties 
Property Value 
______________________________________ 
Brominated 
Resin DPE-BHCB Epoxy 
Laminate Resins Content 
34 40 
Dielectric Properties, @ 1 MHZ 
Dielectric Constant 
3.62 4.55 
Dissipation Factor 0.0033 0.015 
Thermal Properties 175 140 
Glass Transiton Temperature, .degree.C., 
DMA* Damping Peak 
Coefficient of Thermal Expansion, 
124 220 
ppm/.degree.C., Average 50-250.degree. C. 
______________________________________ 
*Dynamic Mechanical Analysis 
As shown in Table 4 above, the dipropargyl ether resin laminates do have 
preferred lower dielectric constants and dissipation factors than the 
standard brominated epoxy resin laminate even at lower resin content. The 
Tg's of the dipropargyl ether-based laminates were also much higher than 
for the standard brominated epoxy resin-based laminate. The coefficient of 
thermal expansion of the dipropargyl ether-based laminates are also lower 
than for the standard brominated epoxy-based laminate.