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Патент USA US2404220

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Patented July 16, 1946
coronmas or mm nsnzmm Ann
vnwr. scam-am
' Gaetano r. D’Alelio, manna, mm'm a»
General Electric Company, a corporation of
New York
No Drawing. Application June 243, 1942,
N0. 448,158
‘30mins. (Cl- 280-86)
This invention relates to the preparation of
Extensive experiments carried out on the poly
merization of divinyl benzene in a dialkyl ben
zene indicate that an insoluble, infusible resin is
synthetic resin compositions and more particu- '
larly to the preparation of heat-convertible, solu
ble,‘ fusible copolymers of divinyl benzene.
obtainedv as a gel when ordinary polymerization‘
methods are employed. This gel formation or
precipitation takes place in a very short time,
e. g., 15-20 minutes. The extreme sensitivity of
It is known that polymerization of compounds
possessing more than one terminal CH2=C<
grouping; providing the system is not conjugated,
results in the formation of a cross-linked, insol
this resin precludes its use in industrial applica
uble, infusible polymer. Examples of such com
pounds are glycol dimethacrylate, diallyl suc
cinate, diallyl phthalate, diallyl maleate, allyl
acrylate, diallyl oxalate, dimethallyl'ether,.etc.
Likewise, such polymers as a rule are rather brit
tions. By means of this invention I may cause
the copolymers to be formed at a much slower
rate. thus providing a greater permissible devia
tion from any calculated time required to give
a maximum yield of partial polymer. The time
tle and low in ?exural and impact strength. Also,
copolymers made with such compounds contain 15 required depends upon the type as well as the
amount of vinyl compound and catalyst present
ing more than one CH2=C< group are infusible
in the solution. I have found that, by varying
and insoluble to a degree proportional to the
my conditions. a partially polymerized product
amount of compound containing a multiplicity
may be obtained in whatever time is desired.
of CH:‘=C< groups. Such copolymers ~cannot be
molded once formed or cast. Divinyl benzene 20 This behavior is entirely unexpected and unpre
polymerized in the usual manner acts in the same _
fashion. When this compound is polymerized an
dictable as can be seen from the following ex
amples. _ In particular in Example 1 the divinyl
benzene solution containing 50 parts divinyl ben
insoluble, very hard, infusible, nonworkable mass
is obtained. copolymers of divinyl benzene’ which -
zene and 0.5 part benzoyl peroxide gelled in 17
nutes and, whereas the vinyl acetate‘ contain
are known are insolubleand infusible. Although 25
ing the varied quantities of benzoyl peroxide
the copolymeric products of this invention are
given in that example polymerizes with almost
' fusibleand soluble, it is a unique property of these
copolymers that they possess heat-convertibility
, and may, therefore, be converted to an infusible,
insoluble material.
I have now discovered that divinyl benzene may
be partially copolymerized to a soluble and fusi
ble heat-convertible copolymer mass, thus mak
ing available for commercial use a product here
tofore inapplicable. The process by which a sol
uble, fusible partial polymer of divinyl benzene
may be isolated from a dialkyl benzene having at
least two carbon atoms in each alkyl grouping
comprises polymerizing the solution of divinyl
explosive violence at re?ux temperatures, the
mixture of the two had an increase in gelation
time from 17 minutes, through 30 and 60 min-‘
80 utes
all the way to 240 minutes.
The actual polymerization of the divinyl ben
zene in its solution in a dialkyl benzene is car
ried out as previously indicated in the presence
of both a catalyst and an inhibitor of polymeriza
85 tion.
Any suitable method may be employed.
However, I prefer to cause polymerization under
the influence of external heat in the presence
of a catalyst for a period substantially less than
benzene in a dialkyl benzene in the presence of 40 that required to cause gelation of ‘the solution.
For purposes of economy and convenience I pre
both a vinyl-type compound, which acts as an
fer to use re?ux temperature and atmospheric
inhibitor, and a catalyst of polymerization, for
pressure although other elevated temperatures
a time less than that required to cause separation
of the polymer. The dissolved partial polymer is
and pressures ranging from subatmospheric to
then precipitated by the addition of a non-sol- 45 superatmospheric pressure may be used. The
partial copolymer of divinyl benzene may be pre
vent or by evaporation of the volatile constit
cipitated from the dialkyl benzene by the addi
tion of some non-solvent, e. g., methyl alcohol,
Present production of divinyl benzene (mono
ethyl alcohol, glycol, etc,
mer) is carried out in such a manner that the
resulting product is an inseparable mixture of 60 For polymerization catalysts in the polymer
ization of divinyl benzene I may use ozone, ozon
ides, inorganic super oxides such as barium per
' oxide, sodium peroxide, etc., aliphatic acyl per
oxides, e. g., acetyl peroxide, lauryl peroxide,
- which there has been no use up until the present
stearyl peroxide, etc., peroxides of the aromatic
about 20—30% divinyl benzene in diethyl benzene.
The present invention isv of special interest be
cause it utilizes this inseparable mixture for
acid series, e. g.. benzoyl peroxide, etc.,‘, ketone
' '
" '
methylene malonic acid.
malonic acids, e. g.,
monoethyi ester, monopropyl
e. g., acetone peroxide, triacetone peare.
joxide, alkyl derivatives or hydrogen
e, diethyl peroxi
monomethyl ester, ester, dimethylester. diethyl
ester,. monobutyl
> ester,vdipropyl ester, monophenyl ester, dipheny'l
ester, etc., and homologues oi! the above radicals
e. g., ethyl hydrogen peroxid
; etc., mixed organic peroxides, e. g., acetyl benzoyl
‘ peroxide, etc., various per compounds such as
and their related compounds.
1 perborates, persulfatcs, perchlorates, etc., alumi
In order that those skilled in the art may better
as the .halides, e. g., aluminum
understand the teachings of the invention the
' chloride, organic and inorganic acids such as
following examples are given.
‘ methacrylic, hydro?uoric, etc.,
Example 1
, num salts such
of the unsaturated acids as, for instance, cobalt
and manganese resinates, linoleates, maleates,
benzoyl ‘
Gelation times were determined for a solution
; etc., hydrogen peroxide, etc. However,
of divinyl benzene in diethyl benzene for increas
Any suitable
‘ peroxide is a preferred catalyst.
ing concentrations of vinyl acetate.
j amount of catalyst may be used but, in
1 the catalyst concentration will be within the
Parts or Divinyl Vinyl Benso l Gelation
1 range of 0.1-2.0% by weight of divinyl benzene._
23% sol'n benzene acetate peroxi 0 time
of the partial
As inhibitors in the preparation may use with
polymerizates or this invention 1
divinyl aryl derivatives compounds of the type
...... ..
0. so
0. 2a
7 25
The inhibiting e?ect of vinyl acetate is readily
a member of the class consisting of
where X is
hydrogen and ‘halogen and alkyl, aryl,‘ carbo
alkoxy, carboaroxy. radicals, including those
seen from the foregoing chart.
Inporder to isolate the soluble, fusible partial
from any of the above compositions the
re?ux times in each case are reduced sufficiently
radicals in which one or more hydrogen atoms
to‘ prevent gelation. The viscous solution of the
partial polymer is poured into methanol and the
have been replaced by some substituent grouping,
e. g., a halogen and x' is a member of the class
consisting of .halogen and aryl, carboalkoxy, 80 precipitate removed, dried and ground. The
nitrile, and acyloxy radicals includ
product so obtained is soluble in the usual hydro
ing substituted aryl, carboalkoxy, carboaroxy and
carbon solvents and completely fusible. The
polymerizate contains some vinyl acetate inter
acyloxy, e. g., halogen-substituted.
Illustrative examples of the radicals represented
polymerized with divinyl benzene partial polymer.
by X and X’ in the above formula are alkyl, e. g.,
methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
amyl, isoamyl, hexyl, cyclopentyl, cyclohexyl,
methylcyclopentyl, methylcyclohexyl, benzyl,
phenethyl, etc., aryl, e. g., phenyl, tolyl, xylyl,
xenyl, naphthyl, ethylphenyl, methylnaphthyl,
Example 2
I may also make a partial copolymer using
a composition of the type: -
Styrene ___________ -1 __________________ __ 50
etc., carboalkoxy, e. g., carbomethoxy, carbo
Divinyl benzene (217 parts of ‘23% solution
ethoxy, carbopropoxy, carbobutoxy, carboiso
in diethyl benzene)‘ __________________ -_ 50
carbocyclohexoxy, '
butoxy, carbocyclopentoxy,
carbochloroethoxy, carbobromocyclopentoxy, etc.,
carboaroxy, e. g., carbophenoxy, carbotoloxy,
Benzoyl peroxide _____________________ ___ ‘ 0.5
carbo?uorophenoxy, etc., acyloxy, e. g., acetoxy,
, propionoxy.
' Parts by weight
butyroxy, isobutyroxy, cyclopentan
whichingredients are re?uxed short oi’ gelation,
the polymer precipitated and isolated as in-Ex
ample 1.
In preparing the heat-convertible, soluble, ins-1,
oxy, cyclohexanoxy, benzo-oxy, toluoxy, naphtho 60 ible copolymers of divinyl benzene, I'may like
wise use auxiliary inhibiting materials such as
oxy, phenacetoxy, phenpropionoxy, chloropro
carbon tetrachloride, copper, sulfur, hydroxyl
pionoxy. bromocyclopentanoxy, ?uor'obenzo-oxy,
compounds, amines, as disclosed in my copend
iodotoluoxy, etc., and homologues of the forego
ing application Serial No. 448,158, ?led concur»,
' ing radicals.
Illustrative examples oi! the compounds which 55 rently herewith, now U. 8. Patent 2,363,836, is
sued Nov. 28, 1944, or- certain allyl derivatives,
I may use to prepare the soluble, fusible copoiy
for example, their alcohols, aldehydes, ketones,
mers of divinyl benzene are: vinyl halides,'e. g.,
esters, etc., many examples oi! which are given
vinyl chloride, vinylidene chloride, vinyl bromide,
in my copending application Serial No. 448,155,
vinyl iodide, vinylidene bromide, etc., acrylic
‘acids, e.,g., acrylic acid, methacrylic acid, chloro 60 now U. 8. Patent 2,378,195, issued June 12, 1945,
both applications being assigned to the same as
signee as the present invention.v Typical exam
ples are given below.
acrylate, ethyl acrylate,
methyl chloroacrylate, pmpyl acrylate, isopropyl
Example 3
acrylate, butyl acrylate; isobutyl acrylate, iso 65
butyl methacrylate, bromoisobutyl acrylate,
phenyl acrylate, ?uorophe'nyl acrylate, benzyl
acrylate, benzyl methacrylate, ethyl chloroacry
late, etc., aryl ethylenes, e. g., styrene, methyl
Parts by weight
Divinyl benzene (196 parts or 23% solu
tion in diethyl benzene) ....... -.-..--.‘..- 45
Styrene _
-styrene, tolyl ethylene, bromotolyl ethylene, etc., 70 Allyl chloride
Benzoyl peroxide
vinyl esters, e. g., vinyl acetate, vinyl propionate,
vinyl butyrate, vinyl isobutyrate, vinyl valerate,
vinyl cyclopentanoate, vinyl cyclohexanoate, vinyl
The above ingredients were heated at the boil
ing point of‘the reacting mixture for 55 minutes.
benzoate. vinyl methylbenzoate, etc., nitrile‘ de
The solution containing the partial polymer was
rivatives of acrylic acid, e. g., acrylonitrile, meth 75 poured into methanol. The product was tritu
' acrylonitrile, etc., malonic acids and esters, of
rated, dried and ground. when submitted to a
hot plate test at 140° C., the partial polymer was
Example 7
easily fusible.
> Parts by weight
Styrene ____
Example 4
Divinyl benzene (43.5 parts or 23% solu
Parts by weight
Styrene ______________________ ___ ______ __
tion in diethyl benzene) ______________ __ 10
Divinyl benzene (206 parts 01' 23% solu
Benzoyl peroxide ___..______-_________-___
tion in diethyl benzene) _______________ __ 47.5
The above ingredients were heated atthe re
?ux temperature of the reacting'mix'ture for a
period of 15 minutes. The partial polymer was
Allyl acetate _________________________ __ 47.5 I
Benzoyl peroxide __________________ __’___
Methallyl alcohol ___.-. _________________ __ 10
The above ingredients were re?uxed for 35
separatedirorn the solvent by pouring the viscous.
minutes. The product was precipitated by pour-'
solutioninto methanol. The precipitated prod
ing the viscous solution into methanol, thorough
uct was triturated, dried and ground. The usual
ly triturated, and ground. The partial polymer
fusibility was displayed on the hot plate at.
?owed readily when placed on a hot plate at 15 140° C.
140° C.
What I claim as new and desire to secure by
' Example 5
Letters Patent of the United States is:
20 polymerized product produced in accordance
Styrene ; _____________________________ -1 12.5
Divinyl benzene (163 parts of 23% solu
with claim 2.
2. The process which comprises polymerizing
tion in diethyl benzene). ____________ __ 37.5
a composition comprising a solution of divinyl '
benzene in a dialkyl benzene having at least two ‘
Allyl alcohol ____' ________ __~ ___________ __ 37.5
Benzoyl peroxide _____________________ __
l. The heat-convertible, fusible, partially co-.
Parts by weight
25 carbon atoms in each alkyl grouping, in the pres
The above ingredients were heated/at the re
?ux temperature for 40 minutes. The partial '
polymer was precipitated by pouring the viscous
solution into methanol. The product was trit
urated, dried and ground. At the temperature.
ence of both vinyl acetate and a catalyst for the
polymerizationbfor a periodless than required
to cause gelation of the solution, and isolating ‘ .‘
the heat-convertible, fusible, partially polymer-vv
ized product, the vinyl acetate and divinyl ben
of the hot plate, e. g;, 140° C., the resin was 30 zene being present in the said solution in an
easily fusible. »
amount, by weight, corresponding to from 5 to
75 parts of the former to‘ from 50 to 25 parts 01'
~ Example 6
the latter.
Parts by weight
Styrene _______________________________ __ 75
Divinyl benzene (109 parts of 23% solution
in diethyl benzene) __________________ _- 25
Methallyl alcohol ____1 _________________ __ 25
3. The process‘ which comprises polymerizing,
under heat, divinyl benzene in a. diethyl benzene
solution in the presence of benzoyl peroxide and
vinyl acetate for a period of time less than re
quired to cause gel'ation of the solution, the vinyl
The above ingredients were heated at the boil 40 acetate and divinyl benzene being present in the
said solution in an amount, by weight, corre
ing temperature of the reacting mixture for 20
Benzoyl peroxide ______________________ __
sponding to from. 5 to 75 parts of the former to
The partial polymer was precipitated '
from 50 to 25 parts of the latter, and thereafter
by pouring the viscous solution into methanol.
the heat-convertible, fusible, partial
It was then triturated, dried and ground. The 45 isolating
polymer of divinyl benzene so produced.
polymer was fusible at‘ 140° C. 0n the hot plate.
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