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Патент USA US3031299

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3,31,289
Patented Apr. 24, 1962
2
by reacting with dicarboxylic acid, polyethylene glycols
3,031,289
.
SOLID COMPOSITE PROPELLANTS CONTAINING
HETEROPOLYMERIZED POLYESTER RESINS
or polypropylene glycols having the general formula:
Joseph Philipson, Temple City, Calif., assignor, by mesne
assignments, to Aerojet-General Corporation, Cincin
nati, Ohio, a corporation of Ohio
N0 Drawing. Filed Feb. 5, 1951, Ser. No. 209,509
8 Claims. (Cl. 149-—2)
This invention relates to resins and particularly to resins 10 respectively in which n is a whole number ranging from
3 to 7. The molecular weight of such polyethylene
useful as ingredients for rocket propellants.
glycol mixture will ordinarily range from 300 to 650,
The principal object of my invention is to provide poly
and of the propylene‘ glycol mixture, from 425 to
ester resins useful for making copolymers obtained by
700.
vinyl and/or allyl type of copolyrnerization, which have
To permit copolymerization the dicarboxylic acid
good physical properties over a Wide range of tempera 15
should include both saturated and unsaturated dicarbox
tures from substantially elevated temperatures, and which
ylic acid.
when incorporated into a propellant will furnish high
The mole ratio of dibasic acid (saturated dicarboxylic
speci?c impulse.
acid) to unsaturated dicarboxylic acid should be, prefer
Polyesters have heretofore been formed by reacting a
ably, from about 6 to about 15 dibasic acid to about one
polyhydric alcohol with a polycarboxylic acid. To per 20 part unsaturated acid, the optimum ratio being about
mit heteropolymerization with an ole?nic type compound
9 to 1.
the polyester component has some unsaturation, which
The mole ratio of glycol (polyhydric alcohol) to the
is provided by a mixture of unsaturated polycarboirylic
total amount of dibasic acid and unsaturated acid should
acid l or anhydride, and saturated polycarboxylic and/or
be, preferably, from about 0.5 to about 2, the optimum
anhydride. The polyesters are copolyrnerized with a 25 ratio being 1 to 1.
monomeric ole?nic component such as a vvinyl, allyl or
The polyethylene glycol or polypropylene glycol can
be condensed with the dicarboxylic acid in a manner
other ole?n, compatible with the resin. Such resins and
similar to the formation of other polyesters.
propellants containing them are described and claimed in
Examples of dicarboxylic acids that are suitable for
the copending application of Roy Roberts, Serial No.
carrying out this invention are the saturated dicarboxylic
109,409, ?led August 9, 1949, entitled “Propellant Sub
acids such as glutaric, adipic, pimelic, azelaic, sebacic,
etc.; the preferred saturated dicarboxylic acids having be
stance,” and assigned to the same assignee as ‘the present
application. Propellant is made by including an oxidizer,
tween 4 and 10 carbon atoms in the primary chain; and
of the unsaturated polycarboxylic acids which
nitrate, etc., with the resin, to provide the oxygen for 35 examples
are suitable for carrying out this invention are the ali
burning the resin.
phatic unsaturated acids such as maleic, fumaric, citra
Especially good physical properties of the resin are ob
conic, mesaconic and itaconic acid. The anhydrides of
tained by selecting esters of acrylic acid as the ole?nic
maleic, citraconic, itaconic and phthalic acids may also
component. Butyl acrylate is the preferred acrylic acid
be used.
'
ester although other esters can be used to produce resins
The polyesters are normally formed by reacting the
such as ammonium or potassium perchlorate, ammonium
with somewhat inferior’ physical properties. When these
polyethylene or polypropylene glycols having the molec
ular Weight’ in the prescribed range, with the saturated and
materials are copolymcrized with the proper polyesters,
unsaturated dicarboxylic acids. The condensation nor
mally starts at 140° C. and is continued at this tempera
perature. A propellant of unusually high impulse can be 45 ture for approximately 16 hours at which time most of
the water formed by the reaction will have been driven
obtained by using allyl ammonium perchlorate as a com
01f. To insure complete polymerization of the molecule,
ponent of the resin fuel. A propellant combining the de
and to obtain a usable polyester, the polymerization is
sired good physical properties and high impulse is ob
then continued for approximately 72 hours longer at a
tained when the butyl acrylate and the allyl ammonium
perchlorate are both used. Heretofore, when it has been 50 temperature not exceeding 250° C. The preferred tem
perature range at this stage of the condensation is be
attempted to copolymerize polyesters with butyl acrylate
tween 200° C. and 230° C. with the usual temperature
and allyl ammonium perchlorate, it was found that most
about 210° C. The condensation is continued until the
polyesters are not su?iciently soluble in the butyl acrylate
polyester has reached the desired degree of polymeriza
to tolerate the presence of the allyl ammonium perchlo 55 tion as determined by the acid number or viscosity meas
rate. In fact, the presence of allyl ammonium perchlo
urements. The preferred degree of polymerization for
rate tends to make the polyester even more insoluble in
the polyester is between 5 and 100.
butyl acrylate. As a result the ingredients would separate
'EXamples of polyesters formed in this manner are as
a resin results which does not become too brittle at a very
low temperature or show viscous ?ow at a very high tem
and the desired copolym'erization would not occur, or if
follows:
it did occur, the copolymers would be generally, unsatis 60
Resin 1.—-l0.5 moles of polyethylene glycol (molec
ular weight 300), 9:0 moles of adipic acid and 1.0 mole
factory.
-
-'
~
_
,
_
I have found that a polyester resin compounded by
using polyethylene glycols and/or polypropylene glycols,
of maleic anhydride.
'
.
Resin 2.——10.5 moles polypropylene glycol (molecular
weight 425), 9.0 moles of adipic acid and 1.0 mole of
instead of the‘polyhydric alcohols ordinarily used to form
the resin, is'unusual in that it is su?iciently solublein 65 maleic anhydride.
Resin 3.—l‘0.5 moles of polyethylene glycol (molec
n-butyl acrylate to tolerate the presence of allyl ammo
ular weight 300), 9.0 moles of glutaric acid and 1.0 mole
nium perchlorate in substantial quantities‘. Such poly-i
of fumaric acid.
' >
ester resin can be used to provide a series of polyester
copolymers obtained by vinyl and/or allyl type of co
polymerization.
.
.
The polyester resins which I prefer to use are formed
Resin 4.-—l0.5 moles of polyethylene glycol‘ (molec
70 ular Weight 300), 9.0 moles of pimelic acid and 1.0 mole‘
of maleic anhydride.
7
'Resin 5.—l0.5 moles ofpolyethylene glycol (molec
3,031,289
ular weight 600), 9.0 moles of sebacic acid and 1.0 mole
of maleic anhydride.
'
4
polyethylene glycols having a molecular weight of from
about 300 to about ‘650 and having the formula:
Resin 6.—l0.5 moles of polypropylene glycol (molec
ular weight 425), 9.0 moles of azelaic acid and 1.0 mole
of maleic anhydride.
Resin 7.—10 moles of polyethylene glycol (molecular
weight 300), 9.0 moles of adipic acid and 1.0 mole of
maleic anhydride.
Resin 8.——10 moles of polypropylene glycol (molec
wherein n is a whole number from 3 to 7 inclusive, a
mixture of polypropylene glycols having a molecular
Weight of from about 425 to about 700 and having the
formula:
HO—(‘JH—~(CHz—O-—GHr)m—CH-—~OH
ular weight 425), 9.0 moles of azelaic acid, and 1.0 mole 10
CH5
('JHa
of fumaric acid.
wherein m is a whole number from 3 to 7 inclusive, and
Resin 9.-—10 moles of polypropylene glycol (molec
mixtures thereof; dibasic alkanoic acid; and an unsatu
ular Weight 600), 9.0 moles of sebacic acid and 1.0 mole
rated acid selected from the group consisting of lower
of fumaric acid.
alkenoic acids, lower alkenoic acid anhydrides, and mix
All of the above polyesters are su?iciently soluble in 15 tures thereof wherein the mole ratio of dibasic acid to
n-butyl acrylate to permit copolymerization with a vinyl
unsaturated acid is from about 6 to about 15 parts di
and/ or allyl compound in the presence of substantial per
basic acid to about one part unsaturated acid and the
centagesof allyl ammonium perchlorate. For example,
mole ratio of glycol to the total amount of dibasic and
compositions can be compounded within the range shown
unsaturated acid is from about 0.5 part to about 2 parts
20
below:
glycol to about one part dibasic acid and unsaturated
Percent by weight
Esters of acrylic acid _____________________ __ 30-50
Polyesters of the type described above _______ _.. 25~35
acid.
2. A solid propellant resin formulation comprising
from about 30% to 50% n-butyl acrylate, from about
Methyl acrylate
5-15
5% to 15% methyl acrylate, from about 5% to 10%
Diallyl diglycollate _______________________ __- 5-10 25 diallyl diglycollate, and from about 5% to 15% by weight
Allyl ammonium perchlorate ______________ __ 5-15
of the total resin formulation of allyl ammonium per
The following composition produces a satisfactory
chlorate heteropolymerized with from about 25% to 35%
by weight of the total resin formulation of alkyd resin
copolymer:
Percent by weight
comprising the copolymerization product of a glycol se
N-butyl acrylate _____________________________ __ 4 030 lected from the group consisting of a mixture of poly
ethyleneglycols having a molecular weight of from about
Methyl acrylate _____________________________ __ 8
300 to about 650 and having the formula:
Resin 2 ____________________________________ __ 31
Allyl ammonium perchlorate __________________ __ l0
Diallyl diglycollate ___________________________ __ 5 35
To assist the polymerization about 1.0% by weight of
methyl amyl ketone peroxide can be added to the above
mixture. Other suitable catalysts are the organic per
oxides and peresters, such as for example, tertiary butyl
hydroperoxide, I - hydroxycyclohexyl hydroperoxide - 1, 40
wherein n is a whole number from 3 to 7 inclusive, a
mixture of polypropylene glycols having a molecular
weight of from about 425 to about 700 and having the
formula:
HO-CH-(CHz-O-OHrM-(EH-OH
CH1
CH3
methyl ethyl ketone peroxide, benzoyl peroxide, cumene
hydroperoxide, lauryl peroxide, methyl amyl ketone per
oxide, t~butyl perbenzoate, di-t-butyl diperphthalate, etc.
wherein m is a whole number from 3 to 7 inclusive, and
celerator can be any aluminum, cobalt, or iron organic
salt that is double in the above mixture.
basic acid to about one part unsaturated acid and the
mixtures thereof; dibasic alkanoic acid; and an unsatu
Preferably about ‘0.1% by weight of an accelerator is
rated acid selected from the group consisting of lower
also added to permit polymerization to take place at 45 alkenoic acids, lower alkenoic acid anhydrides, and mix
lower temperatures, as the preferred copolymerization
tures thereof wherein the mole ratio of dibasic acid to
takes place at the lowest possible temperature. The ac
unsaturated acid is from about 6 to about 15 parts di
mole ratio of glycol to the total amount of dibasic and
Where the catalyst and accelerator are both employed 50 unsaturated acid is from about 0.5 part to about 2 parts
the polymerization is started at about 70°—80° F.,' and
glycol to about one part dibasic acid and unsaturated
continues for a suitable time until a substantial poly
acid.
merization has occurred. The temperature is gradually
3. A solid propellant resin formulation comprising
raised to 180° F. At this point the entire mixture will
from about 30% to 50% n-butyl acrylate, from about
have substantially copolymerized.
55 5% to 15% methyl acrylate, from about 5% to 10%
An advantage of my invention is that it is possible to
diallyl diglycollate, and from about 5% to 15% by weight
incorporate into the polymer appreciable amounts of
of the total resin formulation of allyl ammonium per
allyl ammonium perchlorate. This compound substan
chlorate heteropolymerized with from about 25% to 35%
tially assists in developing a high speci?c impulse pro
by weight of the total resin formulation of an alkyd
pellant and in some cases also increases the burning rate 60 resin comprising the copolymer of a mixture of poly
of the propellant. Unless the polyesters are formed with
ethylene glycols having a molecular weight of from about
the polyethylene glycol or polypropylene glycol the miX
300 to about 650 and having the formula:
ture will not copolymerize successfully with n-butyl
acrylate to which there has'been added allyl ammonium
perchlorate.
wherein n is a whole number from 3 to 7 inclusive, a
I claim:
dibasic alkanoic acid, and maleic anhydride wherein the
1. A solid propellant resin formulation comprising
mole ratio of dibasic acid to unsaturated acid is from
from about 30% to 50% lower alkyl acrylate, from
about 6 to about 15 parts dibasic acid to about one part
about 5% to 15% methyl acrylate, from about 5% to
unsaturated acid and the mole ratio of glycol to the total
10% diallyl diglycollate, and from about 5% to 15% by 70 amount of dibasic and unsaturated acid is from about
weight of the total resin formulation of allyl ammonium
0.5 part to about 2 parts glycol to about one part dibasic
perchlorate heteropolymerized with from about 25% to
acid and unsaturated acid.
35% by weight of the total resin formulation of alkyd
resin comprising the copolymerization product of a gly
4. A solid propellant resin formulation comprising
from about 30% to 50% n-butyl acrylate, from about
col selected from the group consisting of a mixture of 75
5
3,081,289
6
5% to 15% methyl acrylate, from about 5% to 10%
diallyl diglycollate, and from about 5% to 15% by
Weight of the total resin formulation of allyl ammonium
perchlorate heteropolymerized with from about 25% to
35% by weight of the total resin formulation of an alkyd
resin comprising the copolymer of a mixture of poly
ethylene glycols having a molecular weight of from about
300 to about 650 and having the formula:
wherein m is a Whole number from 3 to 7 inclusive, 3
dibasic alkanoic acid, and fumaric acid wherein the mole
ratio of dibasic acid to fumaric acid is from about 6 to
about 15 parts dibasic acid to about one part fumaric
acid and the mole ratio of glycol to the total amount of
dibasic and fumaric acid is from about 0.5 part to about
2 parts glycol to about one part ‘dibasic acid and fumaric
acid.
7. A solid propellant resin formulation comprising
10 from about 30% to 50% n-butyl acrylate, from about
wherein n is a whole number from 3 to 7 inclusive, a
5% to 15 % methyl acrylate, from about 5% to 10%
dibasic 'alkanoic acid, and fumaric acid wherein the mole
diallyl diglycollate, and from about 5% to 15% by weight
ratio of dibasic acid to furnaric acid is from about 6 to
of the total resin formulation of allyl ammonium per
about 15 parts ‘dibasic acid to about one part fumaric
chlorate heteropolymerized with from about 25% to 35%
acid and the mole ratio of glycol to the total amount 15 by weight of the total resin formulation of a copolymer
of dibasic and fumaric acid is from about 0.5 part to
of a mixture of polypropylene glycols having a molec
about 2 parts glycol to about one part dibasic acid and
ular weight of from about 425 to about 700 having the
fumaric acid.
formula:
5. A solid propellant resin formulation comprising
from about 30% to 50% n-butyl acrylate, from about 20
5% to 15% methyl acrylate, from about 5% to 10%
diallyl diglycollate, and from about 5% to 15 % by weight
wherein m is a whole number from 3 to 7 inclusive, adipic
of the total resin formulation of allyl ammonium per
acid, and maleic anhydride wherein the mole ratio of
chlorate heteropolymerized with from about 25% to 35%
by weight of the total resin formulation of an alkyd resin 25 dibasic acid to maleic anhydride is from about ‘6 to about
15 parts dibasic acid to about one part maleic anhydride
comprising a mixture of polypropylene glycols having a
and
the mole ratio of glycol to dibasic acid and maleic
molecular weight of from about 425 to about 7 00 having
anhydride is from about 0.5 part to about 2 parts glycol
the formula:
'
to about one part dibasic acid and maleic anhydride.
8. A solid propellant resin formulation comprising
30
wherein m is a whole number from 3 to 7 inclusive, a
about 40% nebutyl acrylate, about 8% methyl acrylate,
about 5% diallyl diglycollate and about 10% by weight
dibasic alkanoic acid, and maleic anhydride wherein the
mole ratio of dibasic acid to maleic anhydride is from
chlorate, heteropolymerized with about 31% by weight
of the total resin formulation of allyl ammonium per
about 6 to about 15 parts dibasic acid to about one part 35 of a copolyrner of polypropylene glycol, having a molec
ular weight of about 425, adipic acid and maleic anhy
maleic anhydride and the mole ratio of glycol to the
total amount of dibasic acid and maleic anhydride is
from about 0.5 part vto about 2 parts glycol to about one
dride wherein the mole ratio of adipic acid to maleic an
hydride is about ‘9 to about 1 and the mole ratio of poly
propylene glycol to the total amount of adipic acid and
maleic anhydride is about 10.5 to 10.
part dibasic acid and maleic anhydride.
-6. A solid propellant resin formulation comprising 40
from about 30% to 50% n-butyl acrylate, from about 5%
References Cited in the ?le of this patent
to 15% methyl acrylate, from about 5% to 10% diallyl
UNITED STATES PATENTS
diglycollate, and from about 5% to 15 % by weight of
the total resin formulation of allyl ammonium per
2,472,963
Singleton et a1. _______ __ June 14, 1949
chlorate heteropolymerized with from about 25 % to 35% 45 2,473,801
Kropa ______________ .. June 21, 1949
by weight of the total resin formulation of an alkyd
2,554,567
Gerhart et al __________ _... May 29, 1951
resin comprising a mixture of polypropylene glycols hav- ~
ing a molecular weight of from about 425 to about 700
having the formula:
OTHER REFERENCES
Vincent: Ind. & Eng. Chem, November 1937, pages
50 1267-1269.
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