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Патент USA US3069383

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United States Patent ‘()?tice
3,069,373
Patented Dec. 18, 1962
2
2
3,069,373
is sometimes possible to attain the desired hydrophobic
character of a conversion system by simply building up
MODIFICATION OF POLYEPOXKDE CONVERSION
SYSTEMS WHTH PETROLEUM RESIN-PHENOL
ADDITION PRUDUCTS
extremely high molecular weights, although this method
is not always applicable. The other method is that ‘of
building into the overall polymeric structure suf?cient
hydrophobic material to repel attraction of water mole
cules by the polar linkages used in polymerizing this
Sylvan Owen Greeniee, 343 Laurel Drive,
West Lafayette, Ind.
No Drawing. Filed Mar. 21, 1960, Ser. No. 16,150
17 Claims. (Cl. 260-28)
system to the insoluble, infusible state. If molecules of
water can make appreciable contact with polar linkages
This invention relates to phenol addition products of 10 in the conversion system, the water then acts as a solvent
unsaturated petroleum resins, reactive mixtures of such
for many elements of deterioration such as oxygen, alkali,
- y, products with polyepoxide, and conversion products of
acids, and salts which will in time destroy the organic ma
such mixtures.
terials. On the other hand, if the overall polymeric struc
While chemically resistant, infusible, insoluble materials
ture is of such hydrophobic character that water cannot
may be prepared from properly formulated polyepoxide 15 make contact with the polar groups, regardless of how
conversion products, many of these formulations based on
sensitive these groups might be to reaction with water or
the commercial polyepoxides leave much to be desired in p ,
the other elements which would be solubilized by water,
resistance to aqueous systems. Such weakness, for ex~
deterioration of the organic material does not occur.
ample, to boiling water and other aqueous systems is often
One of the desirable means of introducing the hydro
exhibited by protective coatings prepared from the reac 20 phobic character to conversion systems would be that
tion of commercial polyepoxide resins with polyamines
of introducing hydrocarbon structure which contains rela
containing active‘ hydrogen directly attached to nitrogen '
tively few polar linkages in the nature of non-carbon link
or with the widely used amino-amides, such as the com
ages. It is, however, often di?icult to ?nd a means of in
mercial products known as “Versamids” prepared from
troducing large portions of hydrocarbon structures into
long chain polymerized vegetable oil acids and aliphatic
' the conversion systems due to the lack of proper func
tionality being present in the hydrocarbon materials.
Another di?iculty encountered in introducing the hydro
phobic type hydrocarbon material into such conversion
polyamines. Such systems which convert to infusible, in
soluble materials through the reaction of an epoxide,
group with an active hydrogen directly attached to a
nitrogen of an amide or amine group result in amide or
systems as the polyepoxide conversion mixtures is that of
amine linkages in the tri~dimensional polymer resulting
simple cases of the reaction of ethylamine with diepoxy
obtaining proper miscibility of all ingredients with each
other.
It is accordingly a primary object of the invention to
butane and acetamid with diepoxy butane,
provide novel hydroxyphenylated unsaturated petroleum
' from the conversion reaction. To illustrate, consider the
35
resins effective, in admixture with polyepoxides to pro
vide hydrophobic conversion systems.
It is an additional object of the invention to provide a
method for the preparation of novel hydroxyphenylated
unsaturated petroleum resins.
It is a more speci?c object of the invention to provide
a method eifective to increase the degree or extent of hy
droxyphenylation of unsaturated petroleum resins.
It is an additional primary object of the invention to
Although the foregoing formulae illustrate the reac—
tions of amides and amines with polyepoxides, in com—
mercial practice the amines and amino-amides are more
complex in that they contain a large number of nitrogen
attached hydrogen groups per molecule-the number of
active hydrogens per molecule normally being at least
three and usually many more than three. It is well known
that the carbon-nitrogen linkage forming a part of the
polymeric structure of the conversion products is one of
the more hydrophilic linkages and in order to give satis-'
factory resistance to aqueous systems the overall polymer
provide a highly hydrophobic polyepoxide conversion
system.
It is a further important object of the invention, to
provide a reactive mixture of polyepoxides with phenol
addition products of petroleum resins which are con
vertible to infusible, insoluble products characterized .by
excellent resistance to aqueous systems.
It is an additional object of the invention to provide a
polyepoxide conversion system characterized by hydro
carbon structures of a type and in an amount requisite to
render such systems hydrophobic.
It is a more speci?c object of the invention to provide
must possess su?icient hydrophobic portions to more than 55
reactive mixtures of hydroxyphenylated, petroleum resins
neutralize the hydrophilic character of the carbon-nitrogen
linkages. In many of the epoxide converting systems
consisting of the reaction of polyepoxides with catalysts
or with other active hydrogen coupling compounds, the
products also lack in the requisite overall hydrophobic 60
with polyepoxides which constitute highly hydrophobic
polyepoxide conversion systems characterized by physical
properties requisite for application as protective coatings,
character to give the desired resistance to aqueous sys_
It is an additional object of the invention to provide
terns. To illustrate, the conversion products prepared
by catalytic polymerization of aliphatic polyepoxides are
conversion products of polyepoxide and hydroxyphenyl
ated petroleum resins.
impregnants, adhesives and molded objects.
usually subject to some deterioration as is often exhibited
It has now been found that certain resinous phenol ad
by a Whitening of the surface when exposed to boiling 65 dition products of unsaturated petroleum resins possess
water.
It is generally known in the art that in order to prevent
unusually high hydrophobic character, possess complete
miscibility with commercial polyepoxide conversion sys
deterioration of protective coatings, and plastic objects
tems and co~react into the polyepoxide conversion sys
in general which are to be exposed to the atmosphere,
tems through reaction of the phenolic hydroxyl group
the plastic system must be of such hydrophobic character 70 with a portion of the epoxide groups so as to give highly
that water is not absorbed by the polymeric structure
hydrophobic polyepoxide conversion systems possessing
through attraction of one of the chemical linkages. It
desirable physical characteristics required for applica
3,069,873
3
tions as protective coatings, adhesives, impregnants and
molded objects.
The hydroxyphenylated petroleum resins contemplated
Reinhold, New York, 1947, pages 296-301. Such ma
terials are thought to contain unsaturated allocyclic hy
drocarbon structures which account for the fairly high
degree of unsaturation. The unsaturated petroleum resi
dues are essentially a by-product of petroleum re?ning,
by the invention are prepared by the reaction of a phenol
-. selected from the group consisting of the monohydric
phenols and the dihydric phenols having at least one un
substituted ortho or para portion on an aromatic nucleus
are readily available at a price of 2;? to about 10¢ per
pound and are offered to the market under trade names
on the basis of speci?cations which are normally restrict
“to which a phenolic hydroxyl group is attached with an
ed to physical data and percent unsaturation. Such ma
unsaturated'petroleum resin having an iodine value of
from about 100 to about 500, an average molecular 10 terials vary from a heavy semi-?owing oil. consistency to
high melting solids and usually are very dark in color
weight of from about 250 to about 2500 and containing
although some of the commercial versions now available
anaverage of at least two double bonds per molecule,
said material containing at least about 2.5% phenolic
are of light color.
7
'
I
Illustrative unsaturated petroleum residues ‘are de
Vhydroxyl ‘by weight, an average of at least about 0.75
phenolic hydroxyl groups per molecule and a total phenol 15 seribed in Table I entitled “Unsaturated Petroleum I-Iy- :
addition of at least about 8% by weight.
Preferred hydroxyphenylated petroleum resins con
drocarbon Resins.” It will be noted that the examples
illustrated in the table have iodine values ranging from
119 to 475, molecular weights ranging from 300 to_690,
7, _ tain atleast about 3.5% by weight phenolic hydroxyl.
‘ Hypdroxyphenyl modi?ed petroleum resins containing 7%
and ole?n double bonds per molecule ranging from 2.76
or more phenolic hydroxyl by weight are readily pre 20 to 6.37. Iodine value (or number) as used in tabulating
, pared, for example, by utilization of dihydric phenols
this data represents the grams of’ iodine absorbed per
100 grams ole?n._ The number of double bonds per
I such as resorcinol. The hydroxyphenylated petroleum
‘ resinsvof particular signi?cance accordingly are charac
molecule would then equal‘
‘terized bya range offrom about 3.5% to about 10% by
Iodine valuegx ‘mnwt
weight phenolic hydroxyl.
25
'
254X 100
TheVhydro/xyphenylated petroleum resins also pref
'_erably.__contain an average of at least about 1.5 phenolic
lhydroxyhgroups per molecule. 7 An appropriate range is
‘,‘from about 1.5 to about 10 phenolic hydroxyl groups per
molecule.
The quantity 254 is the molecular weight of iodine. :The
equivalent weight to ole?n group equals
25 4 X l 00
Iodine value
30
>1(he-preferred'hydroxyphenylated resins also contain
Rat‘ least about 153%, and appropriately from about 15%
The limits on iodine value, molecular weight and num
to about 50% total phenol addition.
The hydroxyphenylated petroleum resins contemplated
;,,_by the invention may be classi?ed in two categories. A
ber of double bonds per molecule as tabulatedin the
35 table are not all inclusive of the operable unsaturated
.1 ‘?rst category is‘used per se to effect conversion of poly
petroleum resins. Petroleum resins of somewhat higher
molecular weight than those reported in the table are
epoxide to infusible products. Inasmuch as the hydroxy
available. The contemplated petroleum residues are
characterized by iodine values within the range 'of 100 to
tively low equivalent weight, resins containing only two 40 500, molecular weight Within the range of 250 to 2500
phenolic hydroxyl groups per molecule can frequently
and of ole?n content amounting to at least two double
_ phenylated petroleum resins are characterized by a rela
.» be utilized to effect conversion of polyepoxides. Hydroxy
phenylated petroleum resins preferred for polyepoxide
bonds per molecule.
.
>
conversion contain at least 2.5 phenolic hydroxyl groups
In the following examples, the “Hydropolymer'-’-~oil
is a low-cost, low-molecular-weight (M.W. about 300)
permolecule.
ethylene polymer produced as a coproduct in the manu
-
.
.1 vHydroxyphenylated petroleum resins of the second
category contain less than about two phenolic hydroxyl
'' groups permolecule and hence are ineffective alone to
. convert polyepoxide.
Such materials do, however, co
facture of ethyl chloride by the Ethyl Corporation. It
is brown in color but can be distilled to give lighter frac
tions. This product consists mainly [of cyclic ole?nic
structures having an average of two- or more double
. react to be chemically bound into converted polyepoxide 50,. bonds per molecule. A substantial portionof these
'systems' and are effective to impart hydrophobic char
acter to such systems.
.. .. .. The, hydroxyphenylated
.
.
_
resins contemplated by this
-' invention are fundamentally distinguishable from the
I previously known materials designated as “phenolated
petroleum resins” described in “Experiment 8” of Patent
7 2,319,386.- Attempts to duplicate such experiment with
wthe petroleum resins contemplated by this speci?cation
. for the'most part resulted in gel formation. The only
' phenolated derivatives formed were obtained in quite 60
low yields and were characterized by a hydroxyl content
of less than-two percent by Weight. Such products do
-- , not uniformily co-react inepoxide conversion systems,
and hence fall outside the scope of this invention.
The unsaturated petroleum resins contemplated for
=_ use in formation of the phenol addition products em
‘ braced by the invention are know to the art. Such resins
. may-be: derived from cracking petroleum and from acid
3’ polymerization of petroleum fractions. The cracking of
double bonds are arranged‘in conjugated diene systems,
suggesting possible uses as a polymerizable material in
inks, core oils, drying oils, and surface coatings.,_ Hydro
oolymer oil alone dries to a hard, non-tacky, resinous
?lm.
.
I
TYPICAL PROPERTIES OF “HYDROPOLYMER”
‘
Flash
point,
°
F.
OIL
(Cleveland
I
Firepoint, ‘’ F. (Cleveland Open
» natureof such unsaturated hydrocarbons is very complex,
H
l-
.
.
.
l
1
Cup) ___________________ _. 203-215 (95-l02° C.)
API gravity at 60/60° F ____ _. 23-24
Speci?c gravity ____________ _.. 0.9l0-0.915
Iodine number (Modi?ed
.
Wijs) ___________________ __ 430-475
Acid number (mg. KOH/ gm.
oil) ___________________ __
1
Ash, weight percent _______ __¢ 0.005—0.0l4
petroleum-ordinarily yields gasoline which contains ap 70 Viscosity, SSU, at 100° F_____ 80-90
.preciable amounts .of polymerizable unsaturates which
must be removed in order to stabilize the gasoline. The
g
Open Cup) _____________ _. 180-190 (82-88” C.)
Non-volatile residue content,
Weight percent (by ASTM
method D154-43) ________ _. 55
,widelyvariedkand not’ completely de?ned as indicated
by Wakeman, The Chemistry of Commercial Plastics, 75 Englerdi'st?lation data:
13,069,373
6
The invention generally contemplates hydroXyphenyl
_ _
Temperature
ated petroleum resins from all the various monohydric
Percent distilled
and drhydric phenols. The essential feature of the phe
oR
2-.
-
15
o g'
nohc reactant is the hydroxyl group hence the presence
5 of the other substituents on the aromatic ring structure
100
1s lmmaterial. Representative preferred phenols include
phenol; the alkyl phenols such as ortho-, meta-, and para
212
____ __
gg-
?g
40:
480
249
2%
2g?
32% 10 cresol; ortho-, meta-, and para-ethyl phenol; ortho-, meta-,
70
'
cresol; ortho-, meta-, and paraethyl phenol; ortho-, meta-,
564
and para-propyl and isopropyl phenol; ortho-, meta-, and
296
gg
and para-phenyl phenol; xylenol; resorcinol; methyl re
‘382
sorcinol; alpha napthol; and beta napthol.
-
Hydroxyphenylated unsaturated petroleum resins are
, Cracking temperature’
The PDQ 40 -s
d
f
1
- d
1 fl . h
d carbon 2h :1 compose no polilmefnzeh o e tmc ya
a5:
s S
r produced 1n accordance with the method of the invention
10 by addition of the phenol reactant to the ole?nrc double
bonds of the resin. As indicated by the ensuing examples
g} are geélerzl ybcy‘zilc m claralc er Dan
'1'[ is appropriate to utilize in the reaction mixture at least
‘n Tag :23? E111 91116 b0“ 6 out Per mdo ecu 6‘ fry‘
about three equivalents of the phenol reactant per each
2131310; ddptrimaln y01 ymevazpotra ionfartlh oXiggena “tmé‘
equivalent of hydroxyphenyl in the hydroxyphenylated
Co i da duona updy . mtg“? do . e oygenilrg 20 petroleum resin product. Preferably from about 4 to
m (211130;:l In S efJekftocfct? 1121.135) u in ar_ cull)? F2168 ' T F about 10 equivalents of the phenol reactant are so utilized.
cal 0 irt‘fv 1%)f tie relied‘ 15 cm ‘Se? u
' yp '
ln'the reaction of phenols with unsaturated petroleum
-
Pr P T165
"1 1 P0 Ym r M Speci?c gravity of 60° F __________ --
7
residues, it appears that the phenol is nuclear alkylated
___-9,554 _ ,_ vby addition at the ole?n group. In most cases a part of
Flash (C.O.C.), deg. F _______________ __‘__-_-_
Fire (C.O.C.), deg. F ______________________ __
195 '2‘) the phenol adds to the Ole?n bond by direct addition to
205
form a phenyl ether group. The reaction to form phenyl
Viscosity, SUS/IOO deg. F _____ _.__-__ ________ __
Viscosity, SUS/ZlO deg. F __________________ __
Pour point, deg. F _________________________ -_
Bromine number __________________________ ....
Iodine number ____________________________ __
Solids content (ASTM D154-43), percent ____ __
Initial boiling point, deg. F __________________ __
230
44
‘
‘
l’
'
ether groups in conjunction with hydroxyphenylation has
'proven to be bene?cial to the characteristics of the modi
-35 3,0 ?ed resins in that their miscibility with both the resinous
80
and’ the nonresinous polyepoxides is greatly enhanced
220
thereby. The enhanced miscibility through the pres
6.8
ence of the phenyl ether groups appears to introduce no
375
physical or chemical Weakness as the phenyl ether group
35 is very stable toward heat and chemical reactivity.
'
l
The ‘Pahalez T651118 emPIPYed 111 the eXamPIFS are
unsaturated hydrocarbon resins the characteristics of
a
Various types of unsaturanon account for the reported
iodine vahles of the petroleum resirm only a portion
>
of such unsaturation is receptive to phenol alkylation
pursuant to the invention. To provide a more accurate
40 measure of the phenol alkylation receptivity of the var
which are given below!
Panarcz
Panarez
220-220 ______ -_
210-225. ____ ._
3-210
Panarez
6.210
.
7.210
.
.
1ous petroleum resins, the max1mum degree of phenol
allcylation under the conditions of the invention was de
termined, and the weight of each resin which adds one
Speci?cations:
Softening point,°F.
lodmenumber'wija
Color, coal tar, mac.
200-220.
140(min_)____ 1400mm
’ mole or phenol was calculated
9.
Color, Gardner, max.
T Mild
numherymun
do were denominated as the
_
-
:The values so derived
alkylatlon equ1va]ent weight
'
‘
‘ ‘
of each resin
and are reported in
the ensumg
Table II.
1'
ypica inspections:
Softening point, ° F.
210.
Iodine number .... ._
160.
Color, coal tar _____ -.
7.
223x332?“ ---- r- 10
N41
égéci?c gravi-t—y-,-éb—/.
9.09.
.
N11.
Trace
Trace
Trace
Petroleum resin
Qic?n t1 Alkj'lation
eqmvalcn
panapol 3E ________________________________ ‘_
.
Sapom?catron num-
heft-sh
50
Log-L
Pounds/gallon at 60°
-
Table II
rppaaaa'fngta' CleandeinhIn” cm‘r'grt" Clear,‘ dark
inspection.
yellow.
amber.
brown.
100
eqmmlcnt
125
Panarcz 8-210.
113
330
Panarez 6_21D_ _ _
17;,
240
12g
5
253
A
55 gem“
121F528“
“‘
Ydmmlymeml -------------------------- --
1Weight of resin per ole?nic double bond as determined from the
iodine value of the resin.
Table I
UNSA’I‘URATED PETROLEUM HYDROCARBON RESINS
Calcu
Petroleum residue and supplier
Percent
non-
Iodine
value on
nonvolatile
Soft. pt. or vise.
volatile
Velsicol Ell-52S (Velsicol Chemical Corporation) ____ --
200
300-400
2. 76
Vclsicol M-144 (Vclsicoi Chemical Corporation).
87. 5
5.0 poises, 9 parts to 1 in toluene...
.
170
300-400
2. 34
55
68
0.5 poise ________________________ ..
1.32 poi‘ s_.__
_
_
430-475
2‘20
Panapol 3E (Amoco Chemical Corporation).
83
148 poiscs. 3.0 pulses at 9 parts to 1 of toluene. .
253
590-600
6. 37
31.6 poises .............................. .123.2 poises ...................... ..
93-105 C (ASTM D36-26) ........ -99-107 0 (ASTM D36-26) ...... _.
93-105 0 (ASTM D36-26) ...... ..
119
19%
220
145
160
590-690
590-090
690
590
670
3.00
4. 88
6.10
3.36
4. 20
CTLA polymer (Enjay Company Incorporated) .... _.
95
81
100
100
100
94
75-80 0 (ball and ring) ________________________ .-
range
lated
average
double
bonds
per mol
Hvdropolymer oil (Ethyl Corporation) ...... -_
PDQ-40 (Sun Oil Company) __________ _.
Panapol 5C (Amoco Chemical Corporation).
Panapol 5D (Amoco Chemical Corporation)...
Panarez 3-210 (Amoco Chemical Corporation).
Panarez 6-210 (Amoco Chemical Corporation).
Panarez 7-210 (Amoco Chemical Corporation)...
100
Molecular
weight
.
.
.
_
3.5 poises, 0 parts to l in toluene ............... -.
‘.300
5. 34
____________________ ..
240 .................... ._
3,069,373
7
8
phenol per each mol to be added as a hydroxyphenyl
group are employed. An examination of infra-red ab
A salient feature of the process of the invention re
sides in the discovery that the relative degree of hydroxy
sorption data on the B133 catalyzed products shows that
~phenylation is a function of the phenol concentration in
the hydroxyphenyl groups contain both ortho- and para
the reaction mixture. The alkylation of phenol with
substituted structures.
Panapol 3E in the presence of boron tri?uoride is di
Aluminum chloride, iron chloride and antimony chlo*
verted predominantly to hydroxyphenylation as the pro
ride are comparable in activity with boron trifluoride and
portion of phenol in the reaction mixture is increased
are employed in a similar manner to give comparable
above about two mols per alkylation equivalent of the
results.
Maximum
hydroxyphenylation
is
achieved
when
resin.
about four mols of phenol per alkylation equivalent of 10 Aluminum phenoxide has also ‘been found‘to ‘be an vex
cellent catalyst for the hydroxyphenylation of unsaturated
resin is utilized. This is representative of a phenomenon
petroleum residues. The aluminum phenoxide catalyst
which generally characterizes the phenol alkylation re
desirably is formed by adding aluminum turnings or foil
actions of the invention as the speci?c phenol and resin
to the phenol to be used in the reaction, and heating with
reactants and catalysts are varied. Accordingly one as
agitation at 150° C. to 250° C., depending on the par
pect of ‘the invention contemplates utilization of at least
ticular phenol employed, until all of the aluminum is dis
about twice the amount of phenol theoretically required
solved. Desirably, aluminum is employed in an amount
by the alkylation equivalent of the resin reactant to ef
between 0.1% and 5% by weight of the unsaturated pe
fect predominantly hydroxyphenylation.
troleum residue.
Reactions employing an aluminum
Catalysts which may be employed in accordance with
phenoxide catalyst desirably are carried out in the tem
the invention in the production of hydroxyphenylated 20 perature range of 50° C. to 300° C., depending on the
petroleum resins include Lewis acid type catalysts such as
combination of residue, phenol and catalyst used, the de
boron tri?uoride, aluminum chloride, iron chloride, and
sired characteristics of the ?nal product, and the de
antimony chloride and also aluminum phenoxide and the
composition temperature of the organic components of
various aluminum alkoxides such as aluminum methox
the reaction mixture.
Where ‘the presence of'the small amounts of aluminum
compounds are not harmful to a product in which the
hydroxyphenylated material is to ‘be used, no puri?ca
ide, aluminum ethoxide, aluminum propoxide, aluminum
.isopropoxide and the like. Conversion of such alkoxides
‘to the phenoxide is likely as an excess of the more acidic
phenol is present in the reaction mixtures contemplated.
Boron trifluoride, aluminum chloride, and aluminum
phenoxide are the preferred catalysts.
Of the Lewis acid type catalysts, boron tri?uoride has
30
been found to be particularly convenient. Boron tri?uo
ride can be utilized in relatively small amounts either as
‘the gas or one of the liquid adduc'ts such as the ether
vadduct or the phenol adduct. Regardless of which fonn
is used, the boron tri?uoride would likely form the ad
dition product with phenol in the reaction mixture.
When boron tri?uoride is present in the ‘reaction mixture
tion of the reaction product is required. If desired, the
catalytic activity may be stopped by neutralizing the
aluminum phenoxide with an acid such as a mineral acid
‘or acetic acid. The aluminum may be conveniently re
moved by washing the product (usually solvent solution)
with hot water, and adding a sufficient quantity of neu
tralizing acid to convert the aluminum to a water soluble
salt.
As with ‘the phenol addition products prepared in
the presence of BB,» catalyst, the volatile materials in
cluding unreacted phenol conveniently may be removed
by distillation under reduced pressure while heating the
in ‘catalytic quantities. it is sometimes convenient to carry
pot residual product to keep it su?iciently liquid to facili
out the phenol addition reaction in the presence of an 40 tate agitation throughout the stripping process.
"organic vsolvent such as toluene, xylene, or dichlorodiethyl
An examination of infra red absorption data on the
ether; however, if the polymer is su?iciently low in vis
cosity a ‘solvent is not required. The boron triliuoride
“catalyst may be conveniently removed at the end of the
reaction period by adding water to the reaction mixture.
The water apparently hydrolyzes the boron tri?uoride
thereby terminating its activity. The hydrolyzed boron
tri?uoride may then be removed by washing the product
with hot water. The washing process is also facilitated
by having the polymeric reaction mixture dissolved in an .
organic solvent.
In certain preparations it has been
found advantageous to merely add a small amount of
water to the reaction mixture at the end of the reaction
period, mix thoroughly with ‘heating and stirring, and
?nally remove the water by distillation along with the
unreacted phenol and the organic solvent if a solvent has
been used.
In the preparation of the phenol addition products
using boron tri?uoride catalyst, it has been found de
sirable to carry out the reaction of the unsaturated pe
troleum resin with the phenol in the temperature range
of about 25° C. to 300° 0., preferably about 50° C. to
about 200° C. The temperature and reaction time varies
with the particular combination of phenol and unsatu
rated petroleum resin used as well as the ?nal properties
desired in the phenol addition product.
In general, it has been found that best results are ob
tained when boron trifluoride is employed in a quantity
of at least 0.5% by weight of the unsaturated polymer
employed. Excellent results are obtained when boron tri
fluoride is used in quantities of 0.5% to 5% by weight
of the unsaturated polymer.
aluminum phenoxide catalyzed products establishes that
the hydroxyphenyl groups comprise both ortho and para
alkylation materials with a predominance of the ortho
structure. As with the BE», catalyst the aluminum phen
oxide catalyst gives a good balance between hydroxy
phenylation and phenyl ether formation, thus enhancing
miscibility with hydrocarbon solvents and polyepoxides,
and good reactivity with the e'po'xide groups.
The hydroxyphenylated petroleum resins useful in the
invention frequently demonstrate molecular weights and
melting or softening points which are substantially higher
than might be anticipated from the basic reactions con
templated. Some reactions which account for such vari
ations as well as hydroxyphenyl content of the ?nal
phenol addition products are -'(a) the polymerization of
the ole?n double bond in the presence of a catalyst for
alkylation and (b) the reaction of one phenol molecule
with two double bonds of the unsaturated petroleum
The phenol might, for example, form some di
alkylation product as well as the monoalltylatio-n ma
terial and thus unite two molecules of the petroleum
60 resin.
resin thereby doubling the molecular weight as calculated
without considering such side reaction. The side reaction
of ole?n polymerization in the presence of the alkylation
catalyst would result in increasing the molecular weight
of the ?nal product. Since phenyl ether formation is
possible with the contemplated catalyst, an etheri?cation
of phenol groups already attached to the unsaturated pe
troleum residue through hydroxyphenylation may occur.
Such reaction would also contribute to an increase in mo—
lecular weight.
The detailed procedure followed in preparing the phe
When employing boron tri?uoride catalyst, optimum
nol addition products of the petroleum residues using
results are obtained when a stoichiometric excess of
phenolis present. Desirably, as much as 2 to 3 mols of 75 BFa catalyst as reported in Table Ill is ‘given as follows:
3,069,373
10
The phenol dissolved in the indicated solvent (if sol
to the speci?ed reaction temperature. With all washed
vent is used) and the BF3 ether catalyst are placed into a
batches, suf?cient acid is added to convert the aluminum
3-neck ?ask provided with a thermometer, a mechanical
to a water soluble salt. In cases where the batches are not
agitator, a one-liter dropping funnel, an electrical heating
washed, the aluminum may remain as the phenoxide or it
mantle and a pan of tap water to be used for cooling the
may be neutralized with an acid such as acetic acid so that
reaction if necessary. The reaction mixture is raised to
the aluminum would remain in the product as aluminum
the indicated reaction temperature, and addition of the
acetate.
unsaturated petroleum residue dissolved in the indicated
Illustrative preparations of the phenol addition prod
solvent (if a solvent is used) was begun. The addition of
ucts of unsaturated petroleum resins in accordance with
the unsaturated petroleum residue is at such rate that the 10 the foregoing procedures are described in Table III en'
temperature does not rise above the desired reaction tem
titled “Preparation of Hydroxyphenylated Petroleum
perature from exothermic reaction heat. This addition is
Resins” under Examples 1 through 27.
normally carried out over a period of 10-30 minutes ap
The hydroxyl content of the products identi?ed in
plying heat if necessary or cooling the ?ask externally
Table III was determined by reaction with acetyl chloride
with a pan of tap water if required to hold the reaction
and titrating with alkali. An acetyl chloride-toluene solu
temperature. \At the end of the reaction period, toluene
tion was prepared by mixing 1.5 mols acetyl chloride with
or xylene in an amount approximately equal to the weight
dry toluene to make one liter of solution. Into a 250 ml.
of the reaction mixture is added slowly through the con
iodine ?ask was pipetted 10 ml. of the acetyl chloride
denser. In case solvent has been used in the reaction mix
toluene reagent and the ?ask chilled in ice water followed
ture then this solvent takes the place of a part or all of the 20 by the addition of 2 ml. of pyridine. The ?ask was
solvent required in the washing operation. The solvent
tightly stoppered and shaken to form a paste. Add the
solution cooled to below 90° C. is then washed with water
sample as a 50% solution in toluene in such quantity that
by heating with continuous agitation for 10—l5 minutes at
there remains in excess 0.5 mol of acetyl chloride for
80° C. and allowed to separate into Water and organic . each mol reacted. Gently heat the ?ask for 20 minutes
layers. In case layering is not satisfactory because of 25 in a water bath held at about 60° C. When ?rst placing
emulsi?cation, 20-50 ml. of acetic acid are added to the
the ?ask in the bath, momentarily remove the stopper to
wash. The water layer is removed and the washing with
expel any pressure and reseat ?rmly. Shake the ?ask
80° C. tap water repeated two more times. In some cases
100 ml. of water are added to hydrolyze the B133 as a
several times during the heating period. Remove from
replacement for the three washings. The ?ask is then pro
the water bath and chill in ice water. Add 25 ml. of dis
tilled water and shake well. Add a few drops of phenol
vided with a salt-ice-bath cooled receiver and the mixture
phthalein indicator and titrate with 0.5 N methanolic
heated with rapid agitation until the pot temperature
KOH.
reaches 150~l60° C. at which point the pressure is re
duced to 15-20 mm. of mercury by using a water pump.
The batch is held about 15 minutes at this pressure keep
ing the pot temperature at ISO-250° C. depending on the
are made for any free acidity of the sample and any al
coholic hydroxyl content of the basic polyene used in
A blank is run in a similar manner. Corrections
preparation of the hydroxyphenylated composition.
softening point of the ?nal product (softening points as
used throughout this description are determined by Dur
ran’s Mercury Method, Journal of Oil and Colour Chem
ists’ Association, 12, 173-5 [1929]). In order to keep 40
Percent OH
the hydroxyphenylated petroleum residues sufficiently
from the percent hydroxyl and as tabulated refers to the’
percent hydroxyphenyl or hydroxycresyl depending on the
?uid for good agitation, the pot temperature at this stage
is maintained at an estimated 50° C. above the softening
__ml. for blank——rnl. for sampleX N of KOH><17X100
grams of sampleX 100
The percent hydroxyphenyl (--¢OH) was calculated
point of the ?nal product. The receiving ?ask is then con
speci?c phenol used.
The percent by Weight addition of phenol minus that
nected to a vacuum pump and the pressure reduced to 1-5
added as hydroxyphenyl is represented as phenyl ether
mm. of mercury holding this pressure for 10-15 minutes,
(¢O--), speci?c to the phenol used as with the hydroxy
holding the pot temperature of the constantly agitated
phenyl value.
The calculated minimum molecular weight represents
product at a temperature estimated to be 50° C. above
the softening point. The product is poured into a suit
able container and allowed to cool.
50 a minimum as it did not take into consideration side re
The general procedure used in preparing the phenol
addition products of the unsaturated petroleum resins
using aluminum phenoxide catalyst as reported in Table
III differs from the above procedure for BF3 preparation
actions which tend to increase molecular weights, but
merely took into consideration the percent by weight
added phenol to the original average molecular weight
reported by the supplier on the unsaturated petroleum
residue.
as follows:
The aluminum foil or turnings are dissolved in the phe
nol at a temperature of 150-250" C. as necessary for the
speci?c phenol after which the pot temperature is adjusted
The calculated minimum number of phenolic hydroxyl
groups per molecule is based on the analytically deter
mined hydroxyl content. and the calculated minimum
molecular weight.
Table III
PREPARATION OF HYDROXY PHENYLA’I‘ED PETROLEUM RESINS
Ex.
Grams phenol and ml. solvent
Grams polyene and ml. solvent
No.
Mols
phenol]
Catalyst/100 g.
eq.
polyene
polyene
Hours at; ° C.
Grams
product
750 o-crcsol ____________________ _195 o-crcsol _________ -_
500 (N.V.) Panapol 3E __________ _.
125 (N.V.) Panapol 313..
1.39
1. 45
1.00 g. A1____
1.04 g. A1,..-
645; o-crcsol, 525 xylen
365 (N .V.) Panapol 3E__
1. 65
3.42 ml. BFg-ether... 2.5 at 100-1
230 (N.V ) PDQ-40 _____ __
5.0
2.17 g. Al __________ __
212 (N.V.) CTLA polymer
5.0
2.36 g. A] _______________ __ o ________ __
293
1. 36
1,080 o-cresol _______ __
_____do ___________ __
564 phenol, 525 xvle
365 (N.V.) Panapol 3E_.
_
.
3 at
2 at; 250 ___
3 at 190-195...
850
213
576
293
3.40 ml. BEE-ether"- 2.5 at 100-105-..
560
415 (NlVJ Panapol 3E
2. 58
1.20 g. A1 __________ __ 1.5 at 180-185.._
250 (N.V.) Panapol 3E
_.___do _______________ __
4. 25
4. 25
3.2 g. Al __________ .- 3 at 250 __________________ __
10.0 ml. BFa-ether... ] at 100-105, 2at 120-125 __
671
372
403
200 (N.V.) Panapol 31]-.
_ 226 Panarez 3-210 ________________ __
28" phenol _____________________ .. 439 Velsicol EL 528, 337 aromatic
10.00
1.0
0.87
105 __________ __
355
8.85 ml. BEE-ether"- lat 100-105, 2at120~125
0.68 g. A1 __________ __ 1 at
12.5 ml. BITE-ether... 6 at
28c
53
1.
11
Table Ill-Continued
PREPARATION OF HYDROXY PHENYLATED PETROLEUM RESINS—Continued
Mols
phenol]
Er.
Grams phenol and ml. solvent
Grams polycne and mi. solvent
13.....
188 phenol _____________________ __
254 Velsicol E1. 528 ______________ ..
226 Panarez 3—2l0.__
No.
Catalyst/100 g.
Hours at ° C.
1.0
7.37 ml. BEE-ether...
1 513100-105, 2 at 120-125....
325
1.5
13.3 rrl. BFgethbr... .....do ___________________ __
290
5. 0
17.7 ml. Bits-ether..
1. 73
3.42 rrl. Blkether..
eq.
polyene
polyene
Grams
product
DD
solvent 13.1’. 171-278.
.
‘
-
.
. ._.- do __________________________ ..
. 439 Velsieol EL 528, 525 xylene..-254 Velsicol EL 528 ______________ ..
.-.-.d0
_
1,880 phenol __________________ __ ____ do __________________________ _.
2. 5
11.8 ml. B'Fg-ether ._
5.0
15.75 rrl. BF3-ether._
10. 0
19.7 Irl. BIB-ether..
20..-.. 250 resorcinol, 250 dichlorodi~
250 Velsicol M—144 ______________ -.
21..-..
250 Panarez 6-210 __________________________ ..
2.0 g. Al __________ -.
262 (N.V.) Penapol 5D __________ ..
9.52 ml. BFa-etller...
ethyl ether.
500 p,t-butyl-phenol ___________ .-
22..... 614
biS(4-hydroxyphenyl)
di-
1. 36
2.84
4.0 m1. BFa-ether__-.
methyl methane, 600 dichloro
diethyl ether.
23.._-. 50 phenol, 150 toluene _________ __ 200
0.27
11 g. .4101; ........ .. 0.37 at 10-26, 0.20 at 26-47, ........ .
24..... 188 phenol, 150 toluene ________ __ 50 (N.V.) Pcnapol 3E, 150 toluene.
(N.V.)
Penapol
313,
150
4.0
266
25....- 188 phenol, 200 toluene ________ .. 63.5 Velsicol EL 528, 100 toluene..-
4.0
209 g. AlClz ....... ..
2.5 at 100-105 ____________ ..
84
26....- 330 resorciuol __________________ _. 212 (N.V.) CTLA polymer ______ ..
3.0
4.5 m1. BFa-etl‘er__._ l at 100-105, 2 at 120-125...
276
27 ........ -_do._.-.. ................... _-
3.0
3.811111. BFs-ether..- ----.<1o ............................. ..
toluene.
0.37 at 47~72
261 (N.V.) Penapol 5D .......... -_
Percent by
Ex.
No.
Percent
weight
Soft pt.
phenol
vise.
added
and/or
41. 2 (35. 8)
41. 3 (36. 0)
v102
92
36. 6
21.5
30. 4
34. 8
38. 2
32. 8
38.0
43. 7
18.6
17. 2
21.8
22. 1
22. 3
19. 3
24. 4
26. 4
27. 6
12. 0
28. 4
89
80
85
101
106
104
119
121
176
58
141
168
164
113
131
127
122
100
130
Acid
value
0. 6
0. 4
0. 6
2. 0
2. 0
0
0.16
0. 2
0. 2
1. 8
3.1
1. 1
1. 5
5. 0
6. 2
0. 9
1.8
3. 1
6. 5
1. 4
0. 7
2. 4
Eq. phenol
. Percent
Percent
weight
addition
prep/eq.
addition
as 011
as ——¢OH
as ¢0—
as —-¢OH
phenol in
as ¢O-—
3. 9
4.1
4. 9
21.1
3. 66
3. 5
3. 6
2. 76
weight
28. 2 (20.2)
22. 2 (19. 3)
18. 0
19. 1
56. 4
53. 5
3. 4
3. 78
4. 34
5.05
3. 2
3. 1
22. 8
17. 5
21. 7
14.3
19. 3
23.8
28. 2
27.0
12. 8
10. 5
18.9
16. 0
17. 6
18. 7
20.8
23. 9
27. 8
10.3
27. 4
15. 8
4. 0
8. 7
20. 5
21.0
9. 0
9.8
16. 7
5.8
6. 7
2. 9
6. 1
4. 7
0.6
3. 6
2.5
0
1. 7
1. 0
62. 2
81. 5
70.8
41.0
48.0
72.6
74. 2
61. 9
68. 8
61.0
86. 6
72. 3
79.0
96. 7
85.3
90. 5
100. 0
85. 5
96. 5
4.60
30. 8
3. 42
2. 6
3. 51
4. 16
5.09
4. 91
2. 33
1. 9
3. 43
3. 90
3. 19
used in
‘product
18. 8
7. 1
8. 1
11. 3
8.8
19. 7
5.0
5. 1
3.1
5. 1
9. 2
5. 6
6. 7
11.4
19. 3
3. 9
5. 2
83
Percent
Percent
weight
phenol
AlCls _______ .. 1 at 70-75, 2.5 at 100-105.--
phenol
En.
weight
Min.
Min.
weight
mol.
Incl.
OE/
43. 6
405
1, 090
2.34
46. 5
37. 8
18. 5
29. 2
59. 0
52.0
27. 4
25.8
33. 1
31.2
39. 0
13. 4
27. 7
21.0
3. 3
14.7
9. 5
0
14. 5
3. 5
436
472
616
497
652
485
408
334
346
729
895
495
586
534
500
449
392
336
530
548
1, 092
1, 020
2. 2
2. 13
..-.
_._
982
1, 035
954
1,033
1,138
849
1. 51
2.1
2. 33
3.1
3. 28
1. 16
423
0.47
448
886
S88
0. 91
1. 51
1. 66
424
463
475
483
392
823
0. 85
1.03
1. 21
1. 44
0.74
1. 5
370
3. 1
1.9
10.6
0.44
1. 34
4.84
3. 87
26.7
21. 4
.............................................. ..
13.1
3.0
67 2
87. 5
8v 5
10. 4
32. 8
12.5
6. 6‘
6. 66
21.5
1. 8
92. 6
5. 6
7. 4
2. 6
7. 83
25.3
885
351
439
.................. ..
1,065
463
3.0
1. 1
255 .................. .
217
1 Run in pressure autoclave.
The invention generally contemplates mixtures in all
quantity of polyepoxide used is su?icient to react with the
phenolic hydroxyl groups of the modi?ed petroleum resi
relative proportions of phenol addition products of un
saturated petroleum resins with all resinous and nonresin 50 due, thus giving a chemically integrated conversion prod
uct. In systems using catalysts such as tertiary amines to
ous polyepoxides. Conversion systems containing from
convert the polyepoxide, the quantity of polyepoxide used
about 1 to about 99% by weight of phenol addition prod
is su?icient to react with the phenolic hydroxyl groups
uct and from about 99 to about 1% by weight of poly
of the modi?ed petroleum residue and in addition self
epoxide are speci?cally contemplated. Preferred propor
tions are from about 5 to about 75 percent by weight of
polymerize to give. an infusible, insoluble product. Poly
epoxides possess a very wide variation in epoXide equiv
phenol addition product and from about 25 to about 95
alent weight ranging from 43 for the simplest diepoxide
percent by weight of polyepoxide.
(diepoxybutane) to equivalent weights of several thous
More speci?cally, the parts by weight of the hydroxy
and. As observed from the table entitled “Preparation of
phenylated-phenyletherated petroleum residues and parts
by weight of polyepoxide may be varied widely depend
Hydroxyphenylated Petroleum Residues,” there is con
siderable variation in the functionality of these modi?ed
ing on the particular modi?ed petroleum residue, on the
speci?c polyepoxide, on the type of catalyst or type of
petroleum residues. It will, then, be understood, from the
Wide variation in functionality of the polyepoxides and
active hydrogen coupler used to convert the polyepoxide
and the degree of hydrophobic character desired for the
also of the modi?ed petroleum residues, that by proper
speci?c application. In the case where the polyepoxide
choice of the reactive ingredients. to give the desired in
conversion system consists of a polyepoxide and an active
fusible, insoluble product wide variations in reaction por
hydrogen coupler such as an amino or amino-amide com
pound, the polyepoxide would be used in suf?cient quan
tity to furnish epoxide groups beyond those required to
tions are operable.
Illustrative of the epoxide compositions which may be
. employed in this invention are the complexepoxide resins
react with the active hydrogen on the amino or amino~ 70 which are polyether derivatives of polyhydric phenols
amide coupling compound so as to furnish free epoxide
with such polyfunctional materials as polyhalohydrins,
groups to react with the phenolic hydroxyl groups of the
polyepoxides, or epihalohydrins to form polymeric, poly
modi?ed petroleum residue, thus giving a chemically inte
hydric alcohols having alternating aliphatic chains and
grated conversion'product. In systems using catalysts
aromatic nuclei connected to each other by ether linkages.
such as tertiary amines to convert the polyepoxide, the 75 Typical of these complex epoxide resins are the reaction
3,069,373
"13
"products of bis(4-hydroxyphenyl) dimethyl methane (bis
14
A commercial product of this type is Epon 812 having an
equivalent Weight to epoxide of approximately 150 and
phenol A) with excess ‘molar ,portions of epichlorohydrin.
(In;
'
(n + 1)
marketed by the Shell Ch?l'llillfll Corporation. The prep
on
aration of a large number of these mixed polyepoxides is
described more fully in Zech’s US. Patent 2,581,464._
‘
'
/
Epoxidized polyole?ns such as epoxidized polybutadi
a'lkal'
0+ (72 + aoronionxbnz -——1>
enes described in 2,826,556; 2,829,131 and 2,829,135 was
prise an additional family of aliphatic epoxides useful in
the invention.
Still other aliphatic polyepoxides which have been found
10
ffCH3'
CH3
0
to be valuable in reaction with the resinous polyhydric
O
F
I
0 H2011 H————(l)
-
(?CH2CHOHCHz_-0
/\
O CHzGHCH:
phenols in producing the cured products of this invention
include diepoxybutane, diglycidyl ether, limonene diepox
ide, and diepoxydicyclopentadiene.
Catalysts which are active in inducing the epoxide
15
groups of the polyepoxides to react with the phenolic hy
droxyls of the hydroxyphenylated, phenyletherated poly
mers include alkaline materials such as sodium phen
oxide and organic amines as well as certain acid-type cata
20 lysts such as the mineral acids, boron tri?uoride, alumi
num chloride, and zinc chloride. Preferable catalysts,
As used in the above‘ formula, n indicates the degree of
however, are the alkaline types such as the tertiary amines
polymerization and may have the value of 001' a' whole
which tend to favor the reaction of the epoxide group with
number. Typical-of‘these complex epoxide resins are
phenolic hydroxyl groups as compared to the reaction of
those marketed by the Shell Chemical Corporation under
epoxide group with alcoholic hydroxyl groups, and the
the trade names of Epon 828, Epon 836, Epon 1001, 25 use of these tertiary amines in catalytic quantities induces
Epon 1004, Epon 1007, Epon 1009 and Epon 1031. "
negligible Weaknesses towards water, alkali, and chemical
Another group of resinous polyepoxides useful in re
resistance as a result of the presence of the amine.
action with the hydroxyphenylated polymers are the gly
Generally, it is desirable to employ a conversion tem
cidyl ethers'of phenol formaldehyde condensates.
perature of between about 100 and 250° C.
The epoxide compositions which may be used in pre 30
Table IV, entitled ‘*Polyepoxide Conversion of Hy
paring the compositions of this invention also include
droxyphenylated Petroleum Residues,” describes the prep
aliphatic polyepoxides which may be illustrated by such
aration of some protective coating ?lms from reaction mix
polyepoxides as the polymerization products obtained by
tures containing the hydroxyphenylated petroleum resi
polymerizing epoxyalkyl alkenyl ethers such as allyl gly
dues, a polyepoxide and an epoxide converting agent of
cidyl ether through the unsaturated portions to give the
the catalytic or active hydrogen coupling type. Examples
so-called polyallyl glycidyl ether (PAGE) having a chemi
2a,'3a, 3b, 6a, 6b, 7a, 100, 16a, 16b, and 21a describe heat
cal structure corresponding closely to the following
conversion of some hydroxyphenylated petroleum resi
formula:
v
;
dues.
Viscosities were measured by the Gardner bubble vis
40
cosimeter.
Film hardness was measured with the Sward hardness
rocker setting the value for ?at glass plate at 100.
' GL hardness-adhesion readings are in number of grams
weight required to scratch the ?lm surface in one case and
to completely remove the ?lm from the panel in the other
case as read on the Graham-Linton hardness tester.
The
Graham-Linton instrument provides a means of adjusting
various pressures of up to 2,000 grams on a sharp knife
These products in which 11:0 to about 7 are available in
experimental quantities from the Shell Chemical Corpo
edge placed vertical to the ?lm surface and dragged along
the surface in this position.
ration.
Still other aliphatic polyepoxides which may be used are
factured by Gardner Laboratories, Inc. Wet ?lms of
The bend tests were run using a Mandrel Set manu
‘illustrated by the poly(epoxyalkyl)ethers of polyhydric
0.003" thickness were spread on 30 gauge, bright, dry
alcohols. These polyepoxides for instance, may be ob 55 ?nish, coke tin plates cut to 3 x 5 inch dimensions, cured
tained by reacting a polyhydric alcohol with an epihalohy
by baking as indicated in the tables and bent sharply
drin followed by dehydrohalogenation. Illustrative is
around a steel rod of the size indicated in the column tab
I the reaction, for example, of epichlorohydrin with glycerol
, ulating bend test results.
in the presence of boron tri?uoride to give an intermediate
Other materials and abbreviations used in the tabulated
chlorohydrin which is dehydrohalogenated to give a mixed
data are described as follows:
60,
product represented by the following formula:
_
onion
0
\
CHOH+3CH2CHCH2Cl
H2011
BF,
—->
CHOH
|
NaAlOq
omoomonomol
-—s
I
CH2CHOHCH2C1
/O\
CHgOCHtCHCH:
CHOH
CHzOCHaC'HCHtCl
l
Epon X-701: A liquid polymer of allyl glycidyl ether
described as polyallyl glycidyl ether (PAGE) having an
crnocmcnonctnot
/\
GHnCHCHz
epoxide equivalent weight of approximately 135.
Epon 828: A bisphenol A-epichlorohydrin type poly
vepoxide having a softening point of 8—12‘’ C., and an
epoxide equivalent weight of 190-210.
Asphalt: An asphalt cement of 120/ 150 penetration ob
tained from Socony Mobil Oil Company, Inc.
DMP30: Tris(dimethylaminomethyl) phenolmanutac
70 tured by Rohm & Haas Company.
Versamid 115: A polyamide prepared by the reaction
of polyethylene amines with dimerized vegetable oil acids
to give a viscosity of 500—750 poises at 40° C., an amine
number of 210-230 and produced by the Chemical Divi'
sion of General Mills, Inc.
-
3,089,373
..I
16
Table IV
POLYEPOXIDE CONVERSION OF HYDROXYPHENYLATED .P-E'I‘ROLEUMRESIDUES
Rocker
No.
GL
GL
Viswsitv
Composition of con-
0.003” wet
hard-
suriace ?lm re-
verting mixture
?lm baked
ness
cratch moval
>
Bond test
Color
Solvents and chemicals in hours at
original and
'
after days (d)
1
'
2a.... 50% in xylene, 5
0.5 hour at
parts Example 2,
1 part X-701, 0.06
part DMP30.
100° C.
26
500
1,000
Well converted _____ __ A2, A1 (1d)... H5O, 24+: 50%
150° C.
but brittle.
H2204, 24+;
10% NaOH,
24+, 100% acet—
>
io acid, 24+;
DMF, 24+.
_
3a____
1
25° 0.
40% in xvlene, 4
._.-.d0 ________________________________ __do _______ __
_
parts Example 3,
1 part Epon
X-701, 0.025 part
DM P80.
.
3b____ 42% in xylene, 2
6a____
_.___do_____
78
500.
900
is” ___________ __
18 ;A2, E (1d)___ H2O, 27+; 50%.
parts Example 3,
E2804, 4; 10%
1 part Epon
NnOH, 27+;
X-701, 1 part
Versamid 115.
100% acetic
acid, softens.
40% in toluene, 5
._.__do ___________________________ _.
Well converted
parts Example 6,
1 part Epon
_
A4_
28% NHE, 24+;
acetone, softens;
, toluene, softens;
100% acetic acid,
softens.
___
but brittle.
X-701, 0.03 parts ,
DMP30.
,
6b____ 45% in toluene, 5
_____do_____
50
450
900
parts Example 6,
lé” ......... __.--
" " -
1%}
.'
A2, R (191)". HzO,~69+; 50%
> i
‘I
3 parts Epon
X-70], 2 parts
'
"
-
* H2801, ‘27+;
'
=
]
7a____ 51%in xvlene,-5
’
~
-._-.do.____
parts Example 7,
‘
>
"
40
'
500
>
1,000 ' l/é’?m, ______ -.
'
'
r
' >
1 ‘gal (2d);
g
1a acid‘,'5;‘ ~
; ;
. .HrO,-24+;50%
7
~ . -
X-701, 2 parts
"
'-
'
‘
,
H2SO|,- 1; 100%
1
acetic acid, 1—;
'
DMF, softens,
Versamid 115, 0.08
-
i
part DMP30.
‘
"
'7 "
“
’ 1
10a..- 55% in xylene, 3.5
parts Example 10,
0.25 hour
50
at 150° C.
.
M”
_____ __
'
'4
~
'
4' ‘
parts Example 16,
1 part Epon
4,; ‘
;
100% acetic acid,
-
‘
05 hour at
150° C.
______________________ __
but very
brittle.
.
DMP30.
,
42
500
1, 100
.
,
parts Example 16,
.
-
=
_A,_Z4 (1d)____ HzO,.27+; 50%
~
'
111304,
' I
l 28% NHa,'24+;
-;
_ acetone; softens;
10% NaOH,
X-701, 2 parts
. Versatnid 115, 0.07
100%‘acetic acid,
ie acid, soltens.
softens.
. . ,
64
300
1,100
1%" ........... ..
15
A1, B (1d),
r E (2d).
toluene, softens;
27+; 100% acet-
parts DMP30.
21a..- 48% in xylene, 3
_----d0.__-parts Example 21,
‘ -‘
Wellconverted
X-TOI, 0.03 parts
_____do__..-_
. '
.
toluene,
'
16b___ 45% in xylene, 5
,-
Y 10% NaOVH,
1.7 parts Asphaltl.
16a..- 45% in xylene, 5
'
,HzVQ, 24+; 50%
~
1.5 parts X-701,
2 Parts Epon
96." ’
_' _DME,-1-.
12 BFQ, (1(1),.
' ~
3 parts Epon
acetone; 120+;
, ; 10% NaOH;
' toluene, softens;
, 1 69+; 100%;ac,et-. 1 , 100% acetic acid,
Versamid115,0.08
parts DMP30.
28%,N-H3,_120+;
-
_
H2O, 24+; 50+
H1504,
;
2 parts Epon 823,
10% NaOH,
1 part Versaniid
M+; 100 0
115, 0.05 part
acetic acid, 24+;
DMP30.
‘»
DMF, softens.
1 Asphalt cement of 120/150 penetration obtained from Socony Mobil Oil Company, Inc.
It will be noted as illustrated by Examples 2a’ 3a, 6a
phalts. Appropriate proportions are [from about 90 to
and 16a that conversion products using minor portions
about 10 parts by weight of asphalt or coal tar and from
of polycpoxidcs of high functionality along with the modi
about 10 to about 90 partsby weight of, a conversion
?cd petroleum residues tends to give brittle conversion
products. This brittle character is conveniently over 50 ‘It‘will be observed from the data given on resistance
come, however, by using ?exibilizing converting agents
to chemicals at 100° C. that the converted products pos
such as the Versamids which contribute active hydrogen
scss unusually high resistance to aqueous systems. The
system of the invention.
for conversion of the polycpoxidc and at the same time -
'
i
i
“
‘
‘Y
'
"
plus sign following the‘number of hours signi?es that
contribute a chemically integrated ?exibilizcr. The brit
there was no observable deterioration atthe end of the
tlencss of the reaction products of the modi?ed petroleum 55 test, .while a minus sign indicates that the point of de
residues with polyepoxidcs may also be overcome by using
terioration was inde?nite but below the number given. >
the proper quantity of a polyepoxide which tends to give
In the formulation of products from mixtures of the
?exible system.
modi?ed petroleum residues and polycpoxide conversion
Excellent plasticizers for the conversion systems based
systems it is often desirable to mix these ingredients with
on hydroxyphcnylatcd petroleum residues and polyepox 60 other additives. Such additives may be plasticizers of a
ides are asphalt and coal tar materials. An illustration
of the use of asphalt is given in Example 100:. The out
standing solubility of the hydroxyphcnylatcd petroleum
non-reactive type or those of an active type which com
bine into the system through reaction of active hydrogen
groups contained therein withthe epoxidcs. The additives
may also be pigments and ?llers added to give desired
residues and their conversion products with asphalt is
surprisingly unique and very advantageous from their 165 variations in physical properties and performance. Other
economy and outstanding chemical resistance. It is gen
organic resin forming materials may also be incorporated
erally known that asphaltic materials have outstanding
along with the mixture of modi?ed petroleum residues
and polyepoxides. Typical resinous materials useful in
water and aqueous chemical resistance, however, their
use is normally limited to applications where soft, solvent
this respect include the formaldehyde condensates of
soluble, thermoplastic materials will function. As illus 70 phenols, melamine and urea, polyester resins, alkyd
trated in Example 10a, such materials may now be used
to give formulations capable of thcrmosctting to water
and solvent resistant products. In general the invention
resins, and epoxy resin esters.
I claim:
contemplates mixtures of the conversion systems of the ,
reacting a phenol selected from the group consisting of
invention in varying proportions with coal tars and as
1. A hydroxyphenylated petroleum resin prepared by
175 monohydric phenols and dihydric phenols having at least
3,069,378
17
one of the ortho or para position carbon atoms unsubsti
tuted on an aromatic nucleus to which a phenolic hydroxyl
group is attached, with an unsaturated petroleum resin
having an iodine value of from about 100 to about 500,
an average molecular weight of from about 250 to about
2500 and containing an average of at least two double
18
11. A curable, resinous conversion system comprising
a polyepoxide and a hydroxyphenylated petroleum resin
prepared by reacting a phenol selected from the group
consisting of monohydric phenols and dihydric phenols
having at least one of the ortho or para position carbon
atoms unsubstituted on an aromatic nucleus to which a
bonds per molecule, said material containing at least about
phenolic hydroxyl group is attached, with an unsaturated
2.5% phenolic hydroxyl by weight, an average of at least
petroleum resin having an iodine value of from about
0.75 phenolic hydroxyl groups per molecule and a total
100 to about 500, an average molecular weight of from
phenol addition of at least about 8% by weight.
10 about 250 to about 2500 and containing an average of at
2. The hydroxyphenylated petroleum resin of claim 1
least two double bonds per molecule, said material con
containing at least about 3.5% by weight of phenolic
taining at least about 0.75 phenolic hydroxyl groups per
hydroxyl groups.
molecule and a total phenol addition of at least 8% by
3. The hydroxyphenylated petroleum resin of claim 1
weight.
claiming on the average about 1.5 phenolic hydroxyl 15
12. The conversion system of claim 11 containing from
groups per molecule.
about 5 to about 75% by weight of hydroxyphenylated
4. The hydroxyphenylated petroleum resin of claim 1
petroleum resin and from about 25 to about 95% by
characterized by a phenolic hydroxyl content of from
weight of polyepoxide.
about 3.5 to about 10% by weight, and characterized by
13. The conversion system of claim 11 containing a
a content of from about 1.5 to about 10 phenolic hydroxyl 20 material selected from the group consisting of asphalts
groups per molecule.
5. A process for preparing a hydroxyphenylated pe
troleum resin which comprises reacting of a phenol se
and coal tars.
14. The mixture of claim 13 containing from about
10 to about 90 parts by weight of the conversion system
lected from the group consisting of monohydric phenols
of claim 11 and from about 90 to about 10 parts by
and dihydric phenols having at least one of the ortho 25 weight or" a material selected from the group consisting
or para position carbon atoms unsubstituted on an aro
of asphalts and coal tars.
matic nucleus to which a phenolic hydroxyl group is
15. A cured resinous material formed by the reaction
attached with an unsaturated petroleum resin having an
of a polyepoxide and a hydroxyphenylated petroleum
iodine value of from about 100 to about 500, an average
resin prepared by reacting a phenol selected from the
molecular Weight of from about 250 to about 2500 and 30 group consisting of monohydric phenols and dihydric
containing an average of at least two double bonds per
phenols having at least one of the ortho or para position
molecule, said material containing at least about 2.5%
carbon atoms unsubstituted on an aromatic nucleus to
phenolic hydroxyl by weight, an average of at least about
which a phenolic hydroxyl group is attached, with an
0.75 phenolic hydroxyl groups per molecule and a total
unsaturated petroleum resin having an iodine value of
phenol addition of at least about 8% by weight.
35 from about 100 to about 500, an average- molecular
6. The process of claim 5 wherein the product is char
weight of from about 250 to about 2500 and containing
acterized by a phenolic hydroxyl content of from about
an average of at least two double bonds per molecule,
3.5 to about 10% by weight and characterized by a con
said material containing at least about 0.75 phenolic hy
tent of from about 1.5 to about 10 phenolic hydroxyl
droxyl groups per molecule and a total phenol addition
groups per molecule.
40 of at least about 8% by weight.
7. The process of claim 5 in which the reaction is
16. The cured material of claim 15 containing a mate
carired out in the presence of an acid type catalyst.
rial selected from the group consisting of asphalts and
8. The process of claim 5 in which the reaction is car
ried out in the presence of boron tri?uoride at a tempera
coal tars.
17. The cured mixture of claim 16 containing from
ture of between about 25° C. and about 300° C.
45 about 10 to about 90 parts by weight of the material
9'. The process of claim 5 carried out in the presence
selected ‘from the group consisting of asphalts and coal
of an aluminum phenoxide catalyst at a temperature of
tars and about 90 to about 10% by weight of the poly
between about 50° C. and 300 C.
epoxide hydroxyphenylated petroleum resin mixture.
10. The process of claim 5 in which the phenol is pres
ent in an amount at least about twice that amount theo 50
No references cited.
retically required by the alkylation equivalent of the pe
troleum resin.
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