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Патент USA US3055885

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United States Patent O??ce
1
r
3,955,872
Patented Sept. 25, 1962
2
weight or in poor yields and with properties principally
3,055,872
REEilNOUS REACTIUN PRODUCTS 0F POLYUN
SATURATED ALLYL ESTERS OF ORGANIC CAR
BOXYLHC ACKDS AND A SULFUR CHLORIDE
John L.‘ Lang, Midland, Mich., assignor to The Dow
Chemical Company, Midland, Mich., a corporation of
Delaware
No Drawing. Filed Oct. 13, 1959, Ser. No. 846,064
10 Claims. (Cl. 260--78.4)
of the ester homopolymer. When more than two moles
of sulfur halide per mole of ester is used, the sulfur
halide in excess is wasted.
The copolymer products of this invention may be pre
pared in a wide variety of properties and capable of di
versi?ed utility. The products range from moldable
materials to cross-linked infusible materials. Products
may also be prepared ranging from readily soluble to in
This invention relates to new copolymers and to proc
esses for preparing the same. More particularly it re
lates to such products prepared from allyl esters of or
capable of being molded into articles, extruded into ?bers
soluble in common organic solvents.
The products are
and ?laments, and cast from solution into ?lms and foils.
The advantages and bene?cial results derivable from
ganic acids together with sulfur halides.
This ‘application is a continuation-in-part of US. Serial 15 the present invention will be more apparent from the
following illustrative examples wherein all parts and per
No. 614,052, ?led October 5, 1956.
centages are by weight.
It is the principal object of this invention to provide
a new class of copolymers composed of certain allyl
Example 1
esters of organic acids together with sulfur halides.
Into a vessel containing 22.6 parts of diallyl adipate
It is a further object to provide a process for preparing
such copolymers.
‘
20 there was added portionwise with stirring and cooling 11.2
parts of a mixture of sulfur chlorides having a speci?c
gravity of 1.640 at 15° C. and believed to be composed
of about 71 percent sulfur dichloride and 29 percent sul
It has now been found that new and useful copolymers
fur monochloride. The temperature was maintained be
may be prepared by subjecting a monomeric material 25 low 50° C. throughout the reaction to minimize any free
consisting essentially of a sulfur halide and poly unsatur
radical polymerization. As the addition of the sulfur
ated allyl esters 'of organic acids to polymerization condi
chloride mixture proceeded, the reaction mixture became
tions.
increasingly viscous. When the stoichiometric equiva
The esters useful in this invention are those having at
lent amount of the sulfur chloride mixture is approached
least two ole?nically unsaturated groupings of which at 30 (as indicated by the expressed proportions) the product
least one is an allyl group. Included within the scope
is a straw yellow, very viscous, resinous material.
of the invention are the monoallyl esters of monocarboxy
When suitable free radical polymerization inhibitors are
lic acids, such as the acrylic acids, the diallyl esters of di
employed the same product can be obtained by using tem
carboxylic acids, such adipic and terephthalic acid, and
peratures somewhat above 50° C.
the triallyl esters of tribasic acids such as cyanuric acid. 35
Example 2
When monoole?nically unsaturated esters are used, no
polymeric products are obtained.
The procedure of Example 1 was repeated using 11.2
The useful sulfur halides are those which are capable
parts of allyl acrylate in place of the diallyl adipate. In
of reaction with an ole?nically unsaturated compound.
this reaction there appeared to be a reduced tendency
Other objects will become apparent as the description
proceeds.
Typical examples of such halides are sulfur monochloride
(S2Cl2) and sulfur dichloride (SCl2). Usually the com
pounds as available commercially will contain small but
toward free-radical polymerization. The resulting prod
uct was a yellow, very viscous, polymeric material.
Example 3
signi?cant amounts of one of the other halides and these
mixtures are equally operable to secure the advantages
Triallyl cyanurate, 13.9 parts, was dissolved in 40 parts
of the invention. The oxygen compounds such as sul 45 of dry benzene and to this was added portionwise 7.6
furyl chloride and thionyl chloride do not provide the
polymers contemplated in the instant invention.
The polymerizations may be carried out by bulk or
solution polymerization procedures, the techniques of
parts of the sulfur chloride mixture de?ned in Example 1.
After 7.3 parts of the sulfur chloride mixture had been
added the rate of stirring was increased and then the
remainder added slowly. A suspension of tiny gels re
which are well known. When solution polymerization 60 sulted.
methods are employed, any inert solvent, such as toluene,
When the solvent was omitted the reaction was so
may be used. The choice of solvent will be determined
rapid that the product was a rigid gel.
by economic and hazardous considerations, volatility, and
When the reaction was repeated using amounts of the
other known or easily obtainable properties.
sulfur chloride mixture up to 11.31 parts (stoichiometric
The process is carried out by adding the sulfur halide
amount needed for all bonds) the resulting products were
to the ester alone or in solution, preferably with agita
of varying degree of cross linking.
tion. When both polymerizable components are added
Example 4
initially, the reaction is dii?cult to control and the prop
erties of the products are not reproducible.
The procedure of Example 1 was repeated using 24.6
These reactions are exothermic and have no appreciable 60 parts of diallyl ortho-phthalate in place of the diallyl adi
induction period as is noticed in many polymerization
pate. It was found that in the absence of suitable in
reactions. It is preferred to conduct the reaction at
hibitors the temperature had to be kept below 40° C. if
a temperature less than about 40° C. Although poly
free radical polymerization was to be prevented. When
meric products may be obtained by using higher tempera
the temperature was maintained below 40° C. the product
tures, the low temperatures favor better control of the 65 was a light yellow, resinous polymeric solid.
_ reaction.
When substantially pure sulfur monochloride or sul
The molar ratio of monomeric reactants within which
fur dichloride is substituted in equivalent amount for the
useful polymeric products are obtained is substantially
mixture in any of the above examples, similar polymeric
stoichiometric. When substantially less than one mole of
products result. In all cases the sulfur halide had to be
70
sulfur halide per mole of ester is used, polymeric products
added extremely slowly if light colored products were
are sometimes obtainable but usually of low molecular
to be obtained. When the addition was carried out under
3,055,872
3
conditions so that an excessive temperature occurred the
products were usually dark colored.
What is claimed is:
_
1. As a new copolymeric material the polymerization
product of one molar equivalent of an allyl ester of an
organic carboxylic acid, said ester having at least two
ethylenically unsaturated carbon to carbon linkages, with
from one to two molar equivalents of a sulfur dichloride
product of one molar equivalent of an allyl ester of an In capable of reacting with an ole?nically unsaturated com
organic carboxylic acid, said ester having at least two
ethylenically unsaturated carbon to carbon linkages, with
from one to two molar equivalents of a sulfur halide
pound.
8. As a new copolymeric material the polymerization
product of one molar equivalent of an allyl ester of an
organic carboxylic acid, said ester having at least two
selected from the group consisting of sulfur monochlo
ethylenically unsaturated carbon to carbon linkages, with
10
ride, sulfur dichloride, and mixtures thereof.
from one to two molar equivalents of a mixture of sulfur
2. As a new copolymeric material the polymerization
monochloride and sulfur dichloride capable of reacting
product of one molar equivalent of allyl acrylate with
with the ole?nically unsaturated compound.
from one to two molar equivalents of a sulfur halide
9. As a new copolymeric material the polymerization
selected from the group consisting of sulfur monochlo
product of one molar equivalent of triallyl cyanurate with
15
ride, sulfur dichloride, and mixtures thereof.
from one to two molar equivalents of a sulfur halide
3. As a new copolymeric material the polymerization
selected from the group consisting of sulfur monochlo
product of one molar equivalent of a diallyl ester of a
ride, sulfur dichloride, and mixtures thereof.
dicarboxylic acid with from one to two molar equivalents
10. The process for preparing copolymeric products
of a sulfur halide selected from the group consisting of
comprising the slow addition of from one to two molar
sulfur monochloride, sulfur dichloride, and mixtures 20 equivalents of a sulfur halide selected from the group
thereof.
consisting of sulfur monochloride, sulfur dichloride,
4. The copolymeric material claimed in claim 3,
and mixtures thereof to one molar equivalent of an allyl
wherein said diallyl ester is diallyl adipate.
ester of an organic carboxylic acid, said ester having at
5. The copolymeric material claimed in claim 3,
least two unsaturated carbon to carbon linkages at a tem
wherein said diallyl ester is diallyl terephthalate.
25
perature of less than about 40° C. and allowing the re
6. As a new copolymeric material the polymerization
action to proceed to completion.
product of one molar equivalent of an allyl ester of an
References Cited in the ?le of this patent
organic carboxylic acid, said ester having at least two
ethylenically unsaturated carbon to carbon linkages, with
UNITED STATES PATENTS
from one to two molar equivalents of a sulfur mono
chloride capable of reacting with an ole?nically unsat
urated compound.
7. As a new copolymeric material the polymerization
1,535,740
2,426,994
2,454,862
Snelling _____________ __ Apr. 28, 1925
Frosch ______________ __ Sept. 9, 1947
Collins ______________ _._ NOV. 30, 1948
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