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Патент USA US3038881

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United States Patent O??ce
Patented June '12, 1962
James D. Doedens, Midland, Mich, assignor to The Dow
ghgrnical Company, Midland, Mich, a corporation of
fatty amide condensates, exempli?ed by
e aware
cnHaacoN (C2H4OH) 2
No Drawing. Filed Oct. 5, 1959, Ser. No. 844,200
6 Claims. (Cl. 260-37)
. This invention concerns composite structures contain
CH3 ) CgHéSO 3N3.
and the cationic quaternary ammonias, exempli?ed by
10 C12H25(C5H5CH2)——N(CH3)2C1.
ing inert inorganic ?llers compounded with resinous poly
(diphenyl)-type binders, i.e., poly(diphenyl), poly(di
phenylmethane), poly(o-phenylphenol) and poly(p
phenylphenol). It also concerns their method of manu
In accordance with this invention, novel structural mate
rials having desirable physical properties are prepared
MiXtuI'CS Such as ?lat
of sorbitan mono-oleate, polyoxyethylene esters of mixed
fatty and resin acids and alkylamine aryl sulfonates are
particularly advantageous as emulsifying agents for the
The HMDP’s are prepared by reaction of a holo
methylating agent, such as methyl chloromethyl ether,
methyl bromomethyl ether, bis-(chloromethyl)ether, bis
(bromomethyl) ether or a mixture of formaldehyde and
HCl or l-lBr with a diphenyl type compound, as speci?ed,
in the presence of a Friedel-Crafts type catalyst for the
glass mats, ?brous glass cloth, silica, alumina, magnesia, 20 reaction, such as Zinc chloride, aluminum chloride, ferric
etc. with a halomethylated diphenyl type monomer as
chloride, boron tri?uoride, etc. Procedures for carrying
such or in solution or emulsion form, and heating the
out halomethylation reactions are well-known in the art,
mass to liberate hydrogen halide and form a condensed
and can be applied in halomethylating diphenyl type com
resinous binder ?lled with inorganic ?ller.
pounds such as those mentioned above, to obtain HMDP’s
Suitable binders for the practice of this invention in
useful as starting materials in the practice of this inven
clude the condensation products resulting from the reac
tion. See, for example, US. Patent, 2,911,380, ?led
tion of a Friedel-Crafts catalyst and a halomethyl~, i.e.,
August 26, 1955, and Organic Reactions, vol. 1, pages
chlorornethyl- or ‘bromomethyl-diphenyl, diphenylmeth
63-90 (1942). Mono< or poly-HMDP’s or mixtures there
ane, o-phenylphenol and p-phenylphenol, ringing from
of can be obtained thereby, depending upon the propor
their monohalomethyl to their tetrahalomethyl substitu 30 tions of halomethylating agent used, the extent of the
tion products, and including their commercial mixtures
halomethylation reaction and whether steps are taken to
which contain small amounts of non-halornethylated di
separate and purify individual HMDP’s. Residual cata
by a process which comprises combining various inert
inorganic ?llers, such as mica, glass rovings, ?brous
phenyl type compounds. Hereafter diphenyl, diphenyl
methane, o-phenylphenol and p-phenylphenol will be re
ferred to as diphenyl type compounds.
When the monomers indicated are compound with the
indicated ?llers and heat polymerized, hydrogen halide
lyst need not be removed. In fact, it promotes subsequent
polymerization. When it is desired to accelerate the poly
meriz-ation rate, additional amounts of catalyst are added
to the monomer, advantageously to give from a trace up
to about 2 weight percent total, monomer basis. It is
is evolved and solid or foamed condensation products are
not necessary that the HMDP’s be separated or puri?ed.
obtained depending on the halomethyl content of the
On the contrary, mixtures of unseparated and unpuri?ed
monomer, the content of Friedel~Crafts catalyst, the tem
HMDP’s containing up to 50 weight percent of one or
perature and the thickness of the monomer layer. Mon
more unreacted diphenyl type compounds vare commer
omers having up to one halomethyl group per molecule
cially attractive. Such mixtures contain HMDP’s of vary
on a statistical basis give solid products when polymer
ing halornethyl content up to the tetrahalomethylated
ized. Other monomers having more than one halomethyl
product, in addition to unreacted diphenyl type com
group per molecule give foams when polymerized at cur 45 pound. Unreacted diphenyl type compounds enter into
ing temperatures, e.g., between 90° and 400° C., prefer
ably between 100° and 150° C. The monomers can be
used individually or in admixture with one another. A
mixture of mono- and di(halomethyl)diphenyl type com
pounds is particularly advantageous.
The halornethyl diphenyl type compounds, hereafter
abbreviated as HMDP’s, are used as such or in solution
or emulsion form, advantageously containing between 5
the condensation reaction via the Friedel-Crafts method.
The following examples are in illustration of the inven
tion and are not intended to be limitative thereof.
Chloromethyl o-Phenylphenol
This material was dissolved in acetone to give a 35 per
cent solids concentration. The following mixtures there
and 75 weight percent of monomer when a solution is
55 with were prepared.
used; or between 5 and 25 weight percent when an emul
(A) 50 g. Johns Manville No. 7 asbestos and 25 g.
sion is used, the balance being about 75 to 60 weight parts
‘of Water and about 5 to 14 weight parts of an oil'in-water
(B) 25 g. perlite-plaster aggregate (perlite is an 'ex
emulsifying agent. The ?llers are compounded with the
panded volcanic glass) and 50 g. solution.
monomers or their solutions or emulsions, generally to
(C) 75 g. magnesium oxide and 25 g. solution.
provide a resin uptake between 5 and 15 percent, by mix 60 The chlorine content of the monomer was 15.1 per
ing, dipping, spraying and ‘the like, draining, and heating
cent. Its analysis indicated 20~25 percent o-phenyl
phenol, 45—50 percent chloromethyl-, 20—25 percent di
chloromethyl-, 1—2 percent trichloromethyl- and 0-1 per
time sufficient to liberate hydrogen halide and give a con
cent tetrachloromethyl o-phenylphenol.
densation resin. Solutions containing about 5 to 75 weight 65
at a polymerzing temperature ranging between about 90°
and 400° C., preferably between 100° and 150° C., for a
percent monomer in aromatic hydrocarbon or halohydro
carbon solvents boiling between about 40° and 110° C.
are advantageously used in the practice of this invention.
Suitable emulsifying agents include the following well
Chloromethylated Diplzenylmethane
This material was dissolved in methylene chloride to
give a 40 percent solids concentration. The following
known types: alkylaryl sulfonates, exempli?ed by 70 mixtures therewith were prepared:
C12H25—C6H4—$O3Na; fatty alkyl sulfates, exempli?ed
(A) 25 g. perlite-plaster aggregate and 25 g. solution
by C12H25OSO3Na; nonionic esters, exempli?ed by
(B) 75 g. MgO and 25 g. solution
(C) 50 g. asbestos and 25 g. solution
4.5" X 4.5" X 2 mm. and saturated with 30 g. chloro—
methylated diphenyl (15.2 percent chlorine) containing
0.3 g. ZnCl2.
The chlorine content of the monomer was 16.65 per
Its analysis indicated 15-20 percent diphenyl
methane, 40-45 percent chloromethyl-, 25-30 percent
dichloromethyl-, 1-3 percent trichloromethyl and 0-1
for 15 min. at 150° C.
It was then oven cured
The sample was then subjected
to ASTM test D-757-44T. Average burning rate for
?ve samples was 0.1430 inch per minute.
percent tetrachloromethyl-diphenylmethane.
EXAMPLE Diphenyl
The press was closed and the composition
cured at 160° C. for 15 min.
This material was dissolved in methylene chloride to
give a 40 percent solution. Mixtures of the following
Chlorometlzylated Diphenylmethane
were prepared:
The procedure of Example 4 was repeated with the
(A) 25 g. perlite-plaster aggregate and 25 g. solution
(a) A quantity of 35 g. chlorornethylated diphenyl
(B) 75 g. MgO and 25 g. solution
methane (16.65 percent chlorine).
(C) 50 g. asbestos and 25 g. solution
(b) The composition was cured in the press and did
The chlorine content of the monomer ‘was 15.2 per
not need further curing in the oven.
ASTM Test D-757-44T results on ?ve samples showed
50 percent chloromethyl-, 20-25 percent dichlorometh 20 an average burning rate of 0.1741 inch per minute.
yl-, 1-2 percent trichloromethyl- and 0-1 percent tetra~
What is claimed is:
chloromethyl diphenyl.
l. The combination of an inert inorganic ?ller and a
Its analysis indicated 20-25 percent diphenyl, 45
The mixtures of Examples l-3 were made by thor
oughly stirring the dry inorganic materials in the solutions
polymeric Friedel-Crafts condensation product of the
of halomethylated diphenyl, diphenylmethane, o
until each particle was coated. The mixtures were then 25
phenylphenol and p-phenylphenol and mixtures thereof
allowed to stand at room temperature 16 hours to evapo—
having from 1 to 4 halomethyl groups per molecule and
rate the solvent. Individually the mixtures were put in
wherein halomethyl is a member of the group consisting
a 2" X 4” X 5/s" mold, placed in a Carver press and
of chloromethyl and bromomethyl.
cured for 15 min. at 150° C. and 625 p.s.i. In all cases
2. The composition of claim 1, wherein the ?ller is
an extremely hard molded material was recovered from 30
?brous glass.
the press having the following dimensions: 2" X 4” X 1A".
3. The composition of claim 1, wherein the ?ller is
Each of these articles had the strength and appearance
perlite-plaster aggregate.
of transite. All of the binders adhered well and were
insoluble in organic solvents and resistant to bases and
4. The composition of claim 1, wherein the ?ller is
35 exploded mica.
Rate of burning was determined by allowing a 1/2” x
5. The composition of claim 1, wherein the ?ller is
4" X 1A" piece of the molded material to touch an
electrically heated bar which was cherry red (bar sup—
6. Method for making a composite structure of an
plied by 350 watts power) for 3 minutes and measuring
inert inorganic ?ller and .a polymeric diphenyl binder by
the amount of resin burned 01f, sample blackening, etc. 40 condensing at a temperature ranging between 90° and
during this time period. Masonite, transite, and white
400° C. in the presence of a Friedel-Crafts catalyst, a
pine were run in this test also to give comparable results.
Results are summarized in the following table.
monomer of the group of halomethylated diphenyl, di
phenylmethane, o-phenylphenol, p-phenylphenol and
ASTM D-757-44’l‘
Binder 3
N 0.
in ?nal
burn o?
ing of
General Description of Molded Article
CMOPP 15.1% Cl ____ __
asbestos _______ -_
MgO __________ __
10. 8
No ____ __
0. 031
O. 125
gray color, hard, lookslike transits, much the same
5 ___________ _-__do _________________ __ MgO __________ __
0. 031
0. 083
properties as phenolic bonded asbestos.
light yellow color, hard, good bonding.
gray color, hard, looks and acts like transite, much
the same
as phenolic
hard on surface,
inside. asbestos.
_____d0 _______________ __ perlite-plaster___
OMD 15.2% 01...
___ asbestos _______ __
l6. 7
0. 00
O. 145
0. 104
light gray color, hard, good bonding.
looks like transite, hard, strong, difficult to saw.
_ perlite-plaster...
asbestos... _.__
._._ MgO __________ __
16. 7
16. 7
0. 041
0. 00
0. 145
0. 104
0. 150
0. 145
0. 333
0. 166
0. 292
white color, hard on surfaces, softer bonding inside.
white color, hard on surface, softer bond on inside.
light tan in color, hard, good bonding.
1Flamed throughout whole 3 min. of test.
2 Flame went out after 2.5 min. of test.
3 CM OPP = Ohloromethylated o-phenylphenol; OMDPM = chlorome thylated diphenylmethane; OMD =chloromcthylated diphenyl.
When a chloromethylated p-phenylphenol containing
16.8 percent Cl was substituted for the monomer of EX
ample 1, similar advantageous results were obtained.
Chlaromethylated Diphenyl
Four thicknesses of glass cloth were placed in a mold
mixtures thereof having from 1 to 4 halomethyl groups
per molecule and wherein halomethyl is a member of
the group consisting of chloromethyl and bromomethyl
70 in admixture with an inert inorganic ?ller in proportions
at least su?icient to bind said inorganic ?ller.
No references cited.
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