Note: Descriptions are shown in the official language in which they were submitted.
~l~'h~9
This invention relates to a new class of polyesters and to novel
polyurethane-type elastomer binders useful in solid propellants, formed by
reacting the novel polyesters with a diisocyanate.
Recently, a polyurethane-type elastomer binder has been developed
for use in solid propellants. The binder is synthesized by reaction of a
liquid polyester with a diisocyanate. -
According to structure and molecular weight, the kno~n polyesters
presently employed are viscous liquids, solid resins or wax-like products.
Some of these known polyesters are hydroxy-terminated, having a molecular
weight of about 2000, and are obtained through the polymerization of a mixture
of ~-caprolactone and ~-methyl-~-caprolactone in the presence of ethylene
glycol or of glycerol. These polyesters have been used in the manufacture
of polyurethane foam rubber.
Hydroxy-termlnated polyesters are of specific interest in binders
for solid propellants since they are compatible with cyclotetramethylene-
tetranitramine (HMX), nitrocellulose and nitro plasticizers commonly used
in solid propellants. They also exhibit good hydrolytic stability, do not
require anti-oxidants and give good Adhesive properties to a solid load~
Moreover, due to the polymerization method, these polyesters have very low
acidity and a very low moisture content. These properties make it possible
to obtain aluminized propellant compositions containing 8~/o solids 9 exhibiting
a spe~ific impulse of 272 seconds. However, these hydroxy-terminated poly-
esters are generally solids melting at appro~imately 55-60C or liquids too
viscous to accept solid loading of more than 8~/~o
In an attempt to overcome these disadvantages, synthesis of copoly-
mers of lactones e~g. ~-caprolactone with other monomers has been carried
out, in an attempt to obtain hydroxy-terminated polyesters having lower
viscosity at ambient temperature and a glass transition temperature lower
than the homopolymer. It is believed that the use of a comonomer of a
different structure to that of the cr-caprolactone, by introducing substitu~
tion groups in the co-polymer, creates a certain amount of disorder in the
polymeric chain and prevent6 solidification of the co-polyester, most likely
~`3~
by lowering the Van der ~7aals force of the hydrogen bonds.
At present, this type of hydroxy-terminated polyester, specifically
polylactone polyols, are used in the synthesis of polyurethane elastomers.
For example, the NIA ~ polyols PCP0240 and PCP0300 are used as diols and
triols, respectively, in elastomeric binding agents for solid propellants.
However, PCP0240 has a wax-like consistency at ambient temperature, melts
at temperature above 50C and has a viscosity of 0.65 N.s/m at 55 C.
PCP0300 is liquid at ambient temperature and has a viscosity of
22.5 N.s/m2 at 20C. The high viscosity of these products does not allow
for the mixing of alu~ini~ed propellant compositions which contain more than
~0% solids. Moreover, the glass transition temperature (Tg) of polyurethane
elastomers obtained from these products is approximately -70~C, i.e. lower
than that of polyoxypropylene (-40C) and almost as low as polybutadienes
(-78C).
According to one aspect of the invention, novel C-caprolactone
co-polyesters of structural formula I are contemplated,
H(OR30OCR4CO)x OCH2CH2O ~CO(CH2)5 ~ y
wherein R3 is the residual structure of a dlol of structural formula II or a
dehydrated derivative thereof
HO-R-OH II
wherein R is an alkyl group containing 1 to 8 carbon atoms or an alkyl group
containing 1 - 12 carbon atoms having a nitrogen atom in its backbonc; wllcrcln
R4 is the residual structure of a diacid of structural formula III or a
dehydrated derivative thereof
HOOC(CH2) COOH III
m
wherein m is an integer from l to 36;
wherein x is an integer from about 1 to 10; and
wherein y is an integer from about 1 to 10.
According to another aspect of the invention, a process for the
preparation of co-polyester diols of structural formula I is also contemplated
H(OR300CR4CO)X OCH2CH20 [CO(CH2)5 ~ y
~32~
which comprises (a) reacting~-caprolactone or an ~-caprolactone polymer
with the reaction product of
(i) a diol of structural formula II or a dehydrated derivative
thereof
HO-R-OH II
wherein R is an alkyl group containing 1 to 8 carbon atoms or an alkyl group
containing 1 - 12 carbon atoms having a nitrogen atom in its backbone; and`
(ii) a di-carboxylic acid of structural formula III or a dehydrated
derivative thereof -
HOOC(CH2)m COOH III
wherein m i9 an integer from 1 to 36; wherein R3 is the residual structure of
a diol of structural formula II or a dehydrated derivative thereof, R4 is the
residual structure of a diacid of structural formula III or a dehydrated
derivative thereof and x and y are integers of about 1 - 10 and wherein (i)
is an epoxide and (ii) is an anhydride, the reaction is effected in the -
presence of a primary diol as co-catalyst, or
(b) reacting c~-caprolactone with another lactone, in the presence of a primary
diol as co-eatalyst, wherein R3 and R4 are derived from the residual structure
of said another lactone and x and y are integers of about 1 - 10.
The primary diol e.g. ethylene glycol, is not a true "catalyst"
since a reaction does occur between the diol and the monomer and is therefore
referred to as a "co catalyst".
According to yet another aspect of the invention, novel polyurethane
binders u~eful in the production of solid propellants are contemplated, said
binders being formed by reacting one of the aforementioned novel polyesters
with a diisocynate e.g. isophorone d isocynate (IPDI).
Aceording to yet another aspect of the invention solid propellants -`
of high solids loading are eontemplated comprising 12% w/w of a novel poly-
urethane binder as mentioned above and 88% w/w solids ineluding ammonium
perchlorate and aluminum.
In the drawing whieh illustrates embodiments of the invention, `
~igure 1 iB a graph illustrating the determination of moleeular weight, by
GPC~ of various novel polyesters aceording to the invention, and
-- 3 --
1132~0
Figure 2 is a graph illustrating the viscosity at various tempera-
tures of novel polyesters according to the invention.
Figure 1 demonstrates the homogenity of the diffe}ent compounds
synthesized and enables determination of the molecular weight by GPC of the
different polyester diols. The abscissa is the time elapsed (count) to elude
the molecule of a definite size, while the ordinate represents a measure of -
the absorbance of eludate by infra-red or with refractive index determinations.
The graphical results are shown in the tables under weight average (Mw) and
number average (M ) molecular weights.
The viscosity of different synthetic polymers at several tempera-
tures is shown in Eigure 2 and was compared to either Niax Polyol PCP-0300
or Hydroxy terminated Polybutadiene R45-HT. The abcissa on the graph gives the
temperature in Celsius (C) while the ordinate, the viscosity in Newton x
second/meter square (N.s/m2~ that is identical to Pascal x second (Pa.s) -
and ten times greater than poise.
The following examples further illustrate embodiments of the -
invention.
The use of N-methyl-diethanolamine or of polyesteramine (N-8) ~-
(formed from sebacic acid and N-methyl diethanolamine) as initiator of
(~-caprolactone polymerization, has resulted in hydroxyl-terminated polyester-
amines, that are solid at 50 C. r
EXAMPLE I
Preparation of copolyester diols from (N-8) polyesteramine diol and -capro-
lactone.
A mixture of ~-caprolactone (20 moles) with 1.0 mole of (N-8)
polyesteramine diol (produced by the reaction of sebacic acid with (i) N-
methyl-diethanolamine or with (ii) N-methyl-diethanolamine in the presence
of a catalyst (lead-2-ethylhexanoate, or tetraoctyleneglycol titanate, 1%) is
heated under a nitrogen atmosphere. Solid products at ambient temperature
are obtained. The copolyester diols had a functionality varying from 1.6 to
1.8, a Tg of approximately - 70 and a viscosity of 2.3 N.s/m2 at 50C (see
table I).
- 4 - j
Q
,,
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o o E ~ ,~
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æ _
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C ~ E~3 ~' o
O Z ~ o . L:
~o :~ ~ 00 ~o
~J r-l ~ rl C> ~1 ~,
5~
~3~ ~U
Pre~aration of a copolyester diol or triol from Empo ~ dimer 1014 or Empo
trimer 1040 and ~-caprolactone
The copolymerization of ~-caprolactone and a butylene oxide deriva-
tive of Emery Empol dimer 1014 or Emery Empol trimer 1040 gives liquid
copolyester diols or triols. Empol is a trademark for aliphatic dimer acids
of 36 carbon atoms and trimer acids of 54 carbon atoms.
EXAMPLE 2
Diol Preparation: ~
10 moles of C-caprolactone are made to react with one mole of butyl- -
eneoxide derivative of Empol dimer acid 1014 (Emery Industries Inc.). The
reaction is completed after 24 hours at 180C in nitrogen atmosphere, in the
presence of 0.60% lead 2-ethylhexanoate as catalyst. The product obtained
~,
has an hydroxyl equivalent of 1018 and a average molecular weight (Mvpo) of
1950. It has a wax-like appearance at ambient temperature and a viscosity of
0.66 N.s/m at 50 G. The glass transition temperature (Tg) is -70 C.
Triol Preparation:
The hutylene oxide derivative of the Empol trimer 1040 is substitu-
ted for-the derivative of Empol dimer 1014 in a mixture described in the
preceding paragraph and a triol having an hydroxyl equivalent of 783 and a
Mvpo of 2190 is obtained. The viscosity of this product at 20C is 10.1
N.s/m and the Tg -6ac (See table II).
The b~tylene oxide derivative of the dimer or trimer acid may be
represented as a long chain diol or a triol of general formula:
( , 2 ~n 2 2 ,
' C2H5 C2H5
where n = 1 for a diol and n = 2 for a triol and
R2 = backbone of 36 carbon atoms of the dimer acid, from Emery Empol
,
1014 and R2 = backbone of 54 carbon atoms of the trimer acid, from Emery Empol
1040.
- 6 -
i
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Preparation of a copolyester diol from two lactones
The copolymerization of two lactones of different structures r,~as
studied first. The copolyester synthesis from ~-caprolactone with ~-butyro-
lactone (IOCH2CH2CH2CO) or ~-valerolactone (~-CH(CH3)CH2CH2-lO) in presence of
a cationic catalyst, tetraoctyleneglycol titanate, and a co-catalyst, ethylene
glycol, under a pressure of 0.7 MPa, indicates that a small proportion of
these lactones is introduced in the copolymer. On the other hand, a lactone
formed by a six-membered ring, e.g. ~-valerolactone, copolymerizes with the
C-caprolactone under the same conditions. This product is as crystalline as
the caprolactone homopolymer and melts at a temperature of above 50 C.
EXAMPLE 3
-
Preparation of copolyester diols from two lactones.
A monocyclic ether formed by a seven-membered ring, e.g.~-caprolac-
tone, is copolymerized at 180C under a ni~rogen atmosphere, in presence or
0.1% tetraoctyleneglycol titanate catalyst, with a six-membered ring lactone,
a -valerolactone, and two pentagonal lactones respectively, ~-butyrolactone and
~-valerolactone.
While the a-valerolactone easily copolymerizes with ~-caprolactone
creating a solid product, the pentagonal lactones are difficult to polymerize
alone, but in presence of the f-caprolactone these two lactones are sufficiently
integrated into the copolyester to lower the viscosity at 50 C. (See Table III).
J~ l ~
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~ O O O
8 ,~ z
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0 ~ ~ U~ o
3 ~ ~i ~
C~l
o o o
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~ :~ W
J- ~
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~1 ~ ~ ~C
O J~ O ~ ~ ~ ~1
JJ ~ .,
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C . ~ ~C C~i
o .... ~. () 04
~; s ~ ~ ~0
P~ ~ ~C
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~ O a~ a~ o
E~ Z
~3~0
Pre~aration of copol~ester diols from an anhydride, a cyclic ether and
-caprolactone
The reaction of a cyclic ether with a cyclic anhydride forms a poly-
ester. A new family of co-polyesters obtained from a mixture of ~-caprolac-
tone, a cyclic ether and a cyclic anhydride in the presence of a co-catalyst
such as ethylene glycol, and an initiator, such as tetraoctyleneglycol
titanate, results in the co-polyester diol of the following probable
structure, as for examp]e the polycaprolactone-co-3-phenoxypropylene-1,2-
cyclohexene dicarboxylate diol:
(OC~2I}l-ooc n C)-x OCll2cH2o- ~CO(CH2)50 ) H
CH2oc6H~;
. These copolyesters have a structure which tends to prevent crystallization
and are liquid at ambient temperature. While ~ -caprolactone polymerizes
into a block and while its polymerization rate is independent of the concentrat-
ion of this monomer, the polymeriæation rate of the second monomer is governed
by the rate of condensation of the anhydride with the epoxide.
i EXA~IPLE 4
Preparation of a terpolyester diol from an anhydride, a cyclic ether and
-caprolactone.
A mixture of an epoxide such as phenylglycidyl ether (PGE)~ 1,2-epoxy-
cyclohexene (ECH) or allylglycidyl ether ~AGE) (1,0 mole), a dicarboxylicacid anhydride such as cis-1,2-cyclohexanedicarboxylic anhydride (GHDA),
methylsuccinic anhydride (MSA), 3-methylglutaric anhydride (MGA), pyrotartaric
anhydride (PTA), and phthalic anhydride (PA) (1.0 mole) and ~ -caprolactone
- (1.0 mole), is heated to 140 180 C in nitrogen atmosphere in the presence of
a catalyst tetraoctylene glycol titanate (TOCT), tin dibutyldilaurate
(DGSnDL) or lead 2-ethyl hexanoate (E~lPb), 1.0% in weight of the monomers;
and of a co-catalyst (ethylene glycol, 0.12 mole). The percentage of reactive
anhydride is determined by calc~lating the acid nunnber. An equimolecular
mixture of epoxide and anhydride results in a co-polyester with carboxyl
terminated groups, while an excess of epoxide results in a diol (See Table V).
- 10 -
.
V
The rate of reaction determined by the reduction of the acid number i~ sh~,m
in Table VI. The rate of disappearance of ~ -caprolactone is measured by gas
chromatography.
The polymer obtained by the reaction of PGE, CHDA and ~- caprolac-
tone, polycaprolactone-co-3-phenoxypropylene-1,2~cyclohexylene-dicarboxylate
i9 a homogeneous product, while polymer obtained from AGE, MSA and ~ -capro-
lactone, polycaprolactone-co-3-allyloxy-1,2-proplyene methylsuccinate is a
mixture of two products.
The product obtained from ECH, MSA and ~-caprolactone i.e. poly-
caprolactone-co-1,2-cyclohexylene methylsuccinate is also a homogeneous
product and the molecular weights are calculated by GPC (See Table VII).
EXAMPLE 5
Preparation of a block co-polyester diol, from a diacid, a diol, and a
polymer of ~-caprolactone, namely, polycaprolactone (PCP.
A mixture of a diol (1,2-propanediol, 1.0 mole), a dicarboxylic
acid (adipic, sebacic, 1.0 mole) and polycaprolactone (PCP 0530, 1.0 mole)
is heated at 200-225C under a nitrogen atmosphere in the presence of a
catalyst (TOGT, lppm) until all the acid is completely eliminated. The
residual monomers are evaporated by heating under reduced pressure. The
residual acid contents, hydroxyl group concentration, molecular weight are
then determined by vapour phase osmometer and chromatography on a permeable
gel as well as the viscosity. The results are shown in Table VIII~
- 11 -
113'~1~0
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t~ o ~o
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U~U~ o ~ CO CO CO ~ C`~ o ~
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Z ~ ,~
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~1 X c~( O~ C~l i L
P1, E r- o~ E
hl o` o' ! ~
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r-~ I 'r~ X O~ ~ ~ t
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t' I ¢ ; ~ C ~ O~ r-~ t~. r--¦ O O O O~ t\i L~ ~\l ~ ,
m h t
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h I
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C~ O . ~ ~ ~
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5~ ~ ,~ ;
,~ o ...... ~ .. ~ ..... ..
O ~ r I r~¦ ~ : : : r-¦ r-~ : r-l
P1 I r r--~i r~~ r 1 r-l
O ~ I C~ ~1
r /1~ ~ ~ r~ :
~ ~'~ tr~ t~ r~ tl~ 'C,~ ~ rr~
~ Z ~ t`r~ r~ L.¢
u~ a ~ a~ O~ O r~l ~\1 ~ 1~ ~
ca) 7 ~ ~ ~ ~ N ~ ~ ~ ~ ~ ~ . I
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TABLE ~'l
Rate of reaction of polyester diols
Ratio in ether/anhydride/-caprolactone: 1,5/1,0/1,0 ~ -
:,-,
.-
. .
Time Temp. Anhydride , --
Test No. Reagent sec x 10 3 C
36 PGE~M~CL/~HPb 37 62 180218 9
Zl'6 1l
352~24 1 2
9 ~ ,-
37 PGE~MsA/cL/DBsnDL 2372,6180 73148~9
~I~'8 ~,a ~ .
38 PG-/~FA /CL/TOGT 7,Z 180 56 S
AGE/M5~/~CL/TOGI ~ 0~3 14G 1
~ 46 8 27.7
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- 15 -
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v
EXAMPLE 6
Preparation of a sequenced co-polyester diol from a diacid, a diol and
~-caprolactone.
A mixture of a diol selected from 1,2-propanediol (PG), 1,3-butsne-
diol (13BD) and 3-methyl-1,5-pentanediol (3M15P) (1.1 mole), a dicarboxylic
acid (adipic (AA) or sebacic (SA) 1.0 mole) and ~-caprolactone ~1.0 mole)
is heated to 200-250C in nitrogen atmosphere in presence of a catalyst
(TOGT, boron trifluoride). Volatile products are evaporated through vacuum
heating at 225C. The extent of the reaction is measured by the determination
of the acid group and the quantity of non-polymerized ~-caprolactone. The
hydroxyl concentration, the molecular mass are determined by a vapour phase
osmometry and chromatography on a permeable gel, as well as the viscosity
(see Table VIII). -
Preparation of polyurethane binder from Empol co-polyester diol 1014BO/ ~-CL,
Empol co-polyester triol 1040BO/ ~-CL and a diisocyanate
We prepared elastomers from a mixture of Empo ~ co-polyester diol
1014BO/ ~-CL and Empol~ co-polyester triol 1040BO/ ~-CL. For comparlson
purposes, an elastomer was made from R45M (trade mark for a hydroxy-terminated
polybutadiene sold by Arco Chemical Corp.). These products were transformed
into elastomeric polyurethane by reaction with a diisocyanate. The mixtures
were poured into teflo ~ moulds and placed into a 60C oven to constant shore
A hardness. The mechanical properties of the binders (d , o , ~ , ~ , and E)
were measured at ambient temperature (23C) using a Instron machine (Instron
Canada Ltd., model TTC 111~) on rings manufactured with a punch. These rings
had an interior diameter of 3.17 cm. Samples are drawn at a speed of 0.212
cm/s. The effective gauge length of the te~t tube was 3.50 cm. Mechanical
properties are shown in Table IX. The polyester elastomers have an energy
comparable to polybutadienes. Exemplified diisocyanate are DDI diisocyanate, a
trade mark for an intermediate made from a 36-carbon dimer aliphatic dibasic acid;
acid; isophorone diisocyanate (IPDI); and Isonate 901, a trade name for a
polyfunctional isocyanate from Upjohn Polymer Chemicals of Kalamazoo, ~lichlgan.
- 16 -
. J
1~3~
In Figure 1, the compounds analysed by GPC in curves 1 and 2 ~7ere
obtained by the process reported in Example 6. It is al80 shown in Figure 1
that compounds 3 and 4 had much lower molecular weight (higher GPC counts)
than copolyester diols (curves 1 and 2). It i9 also shown that the copoly-
ester diols (curves 1 and 2) are truly copolymer and not a mixture of polymer
according to the form of the curves (only one peak). The curves of the
additional compounds studied (Emery Empol dimer acid 1014, and hydroxyl
terminated Empol 1014/BO) were given for comparison~
Preparation of polyurethane binders from a terpolymer
diol, from polycaprolactone triol and from diisocyanate
A mixture of terpolymer diol (AGE/PA/~CL) and of Niax Polyol triol
PCP0300 is mixed with a diisocyanate according to the method described in
the preceding paragraph. A mixture of Niax Polyol PCP0240 and PCP0300 was
heated with the same isocyanate for com~arison purposes. The elastomers
obtained have properties similar to those from polybutadienes (Table IX).
~ ~ o
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- 18 -
,
~3~
Preparation of propellant from polyesters
The propellant samples were prepared from ammonium perchlorate
(mixture of 400, 200 and 17 ~m, proportionately weighing 1.7, 2.7 and 1.0
respectively), of aluminum H-15 and of various ingredients used in binders
according to a conventional method. The various ingredients were mixed in a
vertical-propeller mixer of 500 g (Atlantic Research Corp., Alexandria,
(Virginia). To the mixture of polyester diol and plasticizer, we added the
aluminu, the ammonium perchlorate and finally the diisocyanate (table IX)
during a three hour period, mixing constantly at a temperature of 60C, in -
a vacuum. The load was poured into a Teflo ~ mould, which was then agitated
in a vacuum, by a vibrator. It was heated at a constant temperature in an
oven, until the hardness of the sample was constant. The propellant test- -
pieces were then tooled according to JANAF dimensions, and the mechanical
properties in traction were determined following the usual method (3). JANAF
test-pieces, tooled from propellant blocks were used to determine the mechan-
ical properties at 23 C and at -45 C. The mobile apron was moved at a speed
of 0.0847 cm/s and at a deformation rate of 0.0123 s 1. The effective gauge
length of the test-pieces was 8.43 cm. The maximum load and elongation
obtained with the test-piece was determined from the tension-deformation
curve which was used to calculate strain (a ) to maximal elongation (~ ). The
initial modulus was calculated from the slope at the beginning of this same
curve. Results of mechanical properties of the novel propellants are given
in Table X.
Owing to their low viscosity and good compatibility with the plastici-
zer isodecyl pelargonate, two copolyester binders, polycaprolactone-co-propy-
lene sebacate and polycaprolactone-co-3-methyl pentame-thylene sebacate ~batch
69, 93, 102, 104 and 105, Table X) yielded propellants containing up to 88%/N
of solids. The mechanical properties of these propellants were superior to
those obtained from polycaprolactone diols.
~3~1~0
h a~ ~1 ~ O d ~ ~D
1~ ~ O O O O O O O
U~
~ O O o O t~
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~ `D a) a~ t~ `3
E3 t~ ~ ~ ~ c~ t3~ N
~ ~ -1 0 0 ~ _I O ~
w E~ O O O O O O O
ti~
~1 t.~ t~ ~ ~ ~ ~
t b :~ O O O G O O O
h
h tD
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C~ ~1 ~ h ~ P~ n ~
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tD '~ ~ ~d P, .
h O h
C~ O D ,~: t.)
p. ~ h o~ t~4 ~ .
h O O oO ~ ~ _.
~ H t~ I`
~-~ O ~J Yl C) tLI)
~ ~ ~ Z Z
S~ l~t O t.) I t.
r,:~ ~o ~o ~o
tl) C~ tD ¢ ~ o o 1~ ~
09 h ~ tD ~ O O O ~ _I
t~ ht ~ O .-1 ~1 H ~ ~
O ~ tV E3 00 ~ --t E~o o o ~ ~
t ,_1 o p~ o ~ y tJ
I` ~ V~ h _I~Ll Ul Ul w (1
t.~ t 1~ J
O .C h t.~J ' t ~1 ~ ,_1 _I _I
,-1 o tD ~d O ~ t~ O O
t~ ,D
O tii; ~r::: ~ W t~ Q a
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20- ~
The general structural forrnula I was deducted from the apparent
starting materials as set forth in the examples, giving alternate or block
copolymers according to the following Table XI.
TABLE XI
_ _
_ . _ _ _ _ _ _
Epoxides or diols or lactones R3
-- -- . .
1,2-epoxy cyclohexene (ECH) yield 1,2-cyclohexene
4-vinyl-1, 2-epoxy eyclohexene " 4-vinyl-1, 2-cyclohexene
Allyl-glycidyl ether (AGE) " 3-propenyloxy-1, 2-propylene
Phen~l glycidyl ether (PGE) " 3-phenoxy-1, 2-propylene
Polyesteramine diol " CH2-CH2-N(CH~)CH2CH2
N-methyldiethanolamine " N-Methyldiet~eneamine
~-butyrolactone 17 1, 3-propylene
~-valerolactone " 1, 3-butylene
Propylene oxide " 1, 2-propylene
Butylene oxide " 1, 2-butylene
Propylene glycol " 1, 2-propylene
1,3-Butanediol " 1, 3-butylene
3-Methyl-1~ 5-pentanediol " 3-methyl-1, 5-pentamethylene
Niax polyol PCP 0530 " Polycaprolactone
.
Lactones, acids, anhydride R4
-valerolactone yield tetramethylene
~-butyrolactone " 1, 3-propylene
~-valerolactone " 1, 3-butylene
cis-1,3-cyclohexane dicarboxylic
anhydride (CHDA) " 1, 2-cyclohexene
- Methyl succinic anhydride (MSA) " 1, 2-propylene
Methyl succinic acid " 1, 2-propylene
3-methyl glutaric anhydride
(MGA) or acid " 2-methyl-1,3-propylene
Phthallic anhydride (PA) or acid " Phenylene
Adipie acid (AA) tetramethylene
Sebacie aeid (SA) oetamethylene (CH2)8
Empol 1014 C36 radical
From the gel permeation chromatography and nuclear magnetic resonance studies
we can demonstrate the formation of only one copolyester of the written struc-
ture.~ The "x~' units were formqd from a diol and a diacid (or the dehydrated
derivatives) and the llyll units obtained from the ~-caprolactone monomer.
