DTIC AD0825258-THE DEVELOPMENT AND EVALUATION OF A HYDROCARBON BINDER FOR HIGH ENERGY SOLID PROPELLANTS

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~ '
AFR PL-TR-68-9 AGC 1030-83l-7
CJ)
~ THE DEVELOPMENT AND EVALUATION OF A HYDROCARBON
C\1 81 NDER FOR HIGH ENERGY SOLID PROPELLANTS
~
~ by
,. (X)
t
Q R. H. Quacch Ia and A. J. Di Milo
<
I
•
Chemical & Physical Sciences Department
Research &Technology Branch
Aerojet-General Corporation
Sacra men to, California
Quarterly Technical Report AFRPL-TR-68-9
January 1968
This document is subject to special export controla and each tranam1ttal to

foreign governments or foreign nationals may be made only with prior approval of
AFRPL (RPPR·STINFO), Edwards, California, 93523 •
.
'
I
'•
DOC
Sponsore d bY ·o' .I?Jm .nr?rrr
JAN 1 s 1968 II
Air Force Rocket Propulsion laboratory ~~JiS,ii'UGU
Research and Technology Operations
8
Edwards, Callforn Ia 92323 · ..., ... L13>
Air Force Systems Command, United ~~1r Force
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al .aiOI ... "...................... ..

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1 1111 low/at:altiliirf"Oila
Dl:f. Ar~L lld/lr lrdCAl
''When U.s • Government drav'...n1s, specifications, or other

data are used tor &Jll' pUI"',ose other than a detinitel.T
related Government pr~eurement operation, the oo..rnaeDt
thereb)" incurs no reaponsibilitr Dor anr obligation
vhataoeYer, and the tact that the oo..rDMDt •1 ba..
toJ'IIUlated, turniahed, or in &D7 1fllT npplied the laid
drawings, speciticatiol\8, or other data, i• not to be
regarded by il!l)lication cr otborviae 1 or in any unner
licensing the holder or anr other person or corporation,
or con..ying anr riahte or pe1"11111ion to unutacture, ue,
or •ell an;r patented inYention that ..,. in any vq be
related thereto."
•
AFRPL-TR-68-9
THE DEVELOPMENT AND EVALUATION OF A HYDROOARBON BINDER

FOR HIGH ENERGY sor~ID PROPELLANTS
by
R. H. Quacchia and A. J. Di l1ilo
This dooumtnt is subject to special export controls and each transmittal

to toreign Governments or foreign nationals may be made onlY with prior
approval ot AFRPL (RPPR-STINFO), Edwards, California 93S23
AFRPL-TR-68-9
FORE\:IORD
This technical report was prepared under Contract No. AF OL(611)-llL19

as partial fulfillment oi tha requirements or Pro:cet .3Ll8 or the Air r~orce
Rocket Propulsion Laboratory, Research and Techno~ogy Divi~ion, Air Force
Systems Command, Edwards, California. The work reported was done in the
Chemical and Physical Sciences Department of the Aerojet-General Corporation,
Sacramento, California. This report was desicnated Aerojet-Genoral Corporation
Report 10.30-82Q-7 and cov1rs the results of work done during the interval
lL September to 1.3 December 1967. The project was a follow-on to the project
completed under Contract AF OL(611)-lOJ86, the results of which are reported
in AFRPL-TR-67-158. This document reports on Phases Four and Five. This
project was monitored by Mr. Robert Corley.
Acknowledgment is made to the following persons who have contributed '
materially to the work performed during this period: A. J. Hammond, Senior
Chemist, J. L. Humphreys and T. F. Manning, Chemists, F. H. Davidson, Liaison
Engineer, Mechanical Properties Laboratories; and at The General Tire and
Rubber Company to R. G. Chase, Technical Assistant to the Technical Coordinator,
Research and Development. Special acknowledgment is made to Mr. C. Gustavson,
Who is no longer a member of this group, but who contributed significantly to
the work reported here.
Approved By:
-zQ .>?/7 ..
I"C~~ ...... ___,
L. J. Rosen, Manager
1.
Solid Propellant iteseareh Section

Chemical & Physical Sciences Department
Publication or this report does not constitute Air Force approval or

the report's findings or conclusiono. It is published only for the exchange
and stimulation or ideas.
W. H. Ebelke, Colonel, USAF

Chief, Propallnnt Division
Al"RPL-TR-68.?
ABSTRACT
\·lork wa~ continued on the study of Telagen S prepolymers for con-

ventional and advanced propellant systems. The factors affecting low
temperature behavior of conventional systems and a replacement for CTI
received most attention this quarter. Saturation of Telagcn prepolymers
definitely causes poor low temperature properties iu binders and propellants.
This was established by studies with a serie3 of related polymers dtffering
only in saturation. Mixtures of saturated and unsaturated prepolymerr> were
not as good as a partially saturated prepolymer for low ternperature behavior.
Prepolymer molecular w~ight and the nature of the crosslinker had ve~f little
effect on the low temperature mechanical properties. Telagen S prepolymers
have been characterized by chromatography on silica gel. The Esso technique
has been Dimplified and an infrared method was used to follow the function-
ality of the eluted polymer. Preparat.ive chromatography to obtain di-
functional prepolymer for binder and propellant studies was developed. Aging
studies were continued and a~ing of binders with partially saturated pre-
polymers was becun.
The study of advanced systems was continued by model compound and
propellant invest.igations using HDP and HAP. Acetylazetidine and 2,5-di-
oxaspiro[J,J] heptane were incompatible with HAP and only the latter was
compatible with HDP. HO\o~ever the dioxaspiroheptane did no't react ~lith
acid at 50°C. It was observed that HA? and HDP very rapidly dehydrate
secondary alcohols. ':Ji th these materials only primary alcohols may be
used. Some HAP propellants were made.
AFRPL-TR-68-9
TABLE OF CONTENTS
I. INTRODUCTION 1
II. OBJECTIVE 1
III. SUHMARY 1
IV. TECHNICAL DISCUSSION 3
A. Task One 3
1. Introduction 3
2. New Prepolymcrs 3
3. Characterization of Ingredients u
L. Chromatographic Studie3 5
5. Prepolymer runctionality 11
6. Low Temperature Properties 12
7. Replacement of CTI 28
B. Task Two 32
1. Introduction 32
2. ~lodel Studies J2
3. HAP Propellants Ll
L. HDP Propellant L2
c. Task Three L2
1. Introduction L2
2. Preparation of 1-Acetylazetidine L2
D. Task Four L~
1. Introduction LL
2. Effect of PropolyTncr Sot,uration on !-\inder Agin~ LlJ
3. Acing of Con•.rentional Propellants LL
i
AF'RPL-TR-68-9
LIST OF TADLES
Number !_ago
I Properties of Some Telagon S Prepolymers J
II Fractionation of Telagen S 7
III Relation of Relative Intensities or Infrared Bands 9
to Hono- and Di- :r·unctionalit.y for Prepolymer 158H
IV Preparative Chromatography of Prepolymer 158H 9
v Practical Functionality of Telagen S Prepolymers 12
VI Composition and Properties of Tolagen S Binders 13
VII Effect of K1~tures of Unsaturated and Saturated 20
Prepolymere on Low Temperature Behavior or Binders
VIII Compositions and Properties or Propellants Prepared 2L
with Telagen S Prepolymers
IX Compcosit,ions and Properties or Telaeen S Propellants 26
Crosslinked ~ith GTRO
X Relation of Crosslink Density and l1echanical 29
Behavior of Hydrocarbon Binders
XI F~tent ot Reaction ot Dioxaspiroheptane (1.75N) and 33
Propionic Acid (1.75N) in the Presence ot HAP and HDP
( 8~) After 18 Hours in Benzene
XII Reaction of 2-0ctanol (0.88N) with n-1-Decenylsuccinic 3L
Anhydride (0.88N) in tho Presence of HAP and HDP (8'7.C)
nt 23°C in Benzene
•
XIII Reaction or 2-0ctanol (o.88N) with n-1-DecenylsuccinAc 31
.A-:-,iv1rido (o.86N) in the Preocnco ot HDP (80,() at 23 C
und Ethyl N-Phenylcarbamatc in Benzene
XIV Reaction or 1-0ctanol (0.08N) with n-1-Decenylsuccinic 36
Anhydride (O.B8U) in tho Presence of HDP (8Qt) at 23°C
in Benzene
ii
r ...
:
C. :üI I :I?E SECTION •
BUFF S&CTION
iS .ilON
i eu m/tm\M\iffi cofo
AtfAJL and/or SPECIAL
"When U.S. Government drawings, specifications, or other

data are used for any purpose other than a definitely
related Government procurement operation, the Government
thereby incurs no responsibility nor any obligation
whatsoever, and the fact that the Government nay have
formulated, furnished, or in any way supplied the said
drawings, specifications, or other data, is not to be
- -o -v or Xu any
licensing the holder or any other person or corporation,
or conveying any rights or permission to manufacture, use,
or sell any patented invention that may in any way be
related thereto."
AFRPL-TR-68-9
THE DEVELOPMENT AND EVALUATION OF A HYDROCARBON BINDER

FOR HIGH ENERGY SOLID PROPELLAOTS
by
R. H. Quacchia and A. J. Di Milo
This document is subject to special export controls and each transmittal

to foreign Governments or foreign nationals may be made only with prior
approval of AFRPL (RPPR-STINFO), Edwards, California 93523
AFRPL-TR-68-9
FOREWORD
This technical report was prepared under Contract No. AF Oij(611)-III4I9

as partial fulfillment of the requirements of Project 3Ü1Ö of the Air Force
Rocket Propulsion Laboratory. Research and Technology Division, Air Force
Systems Command, Edwards, California. The work reported was done in the
Chemical and Physical Sciences Department of the Aerojet-General Corporation,
Sacramento, California. This report was designated Aerojet-General Corporation
Report 1030-Ö2Q-7 and covers the results of work done during the interval
II4 September to 13 December 1967. The project was a follow-on to the project
completed under Contract AF Oii(6ll)-10386, the results of which are reported
in AFRPL-TR-67-158. This document reports on Phases Four and Five. This
project was monitored by Mr. Robert Corley.
Acknowledgment is made to the following persons who have contributed

materially to the work performed during this period: A. J. Hammond, Senior
Chemist, J. L. Humphreys and T. F. Manning, Chemists, F. H. Davidson, Liaison
Engineer, Mechanical Properties Laboratories; and at The General Tire and
Rubber Company to R. G. Chase, Technical Assistant to the Technical Coordinator,
Research and Development. Special acknowledgment is made to Mr. C. Gustavson,
who is no longer a member of this group, but who contributed significantly to
the work reported here.
Prepared By: Approved By:

~?
c *>
A. T. Di Milo L. J. Rosen, Manager
Program Manager Solid Propellant Research Section
Chenical "< Physical Sciences Department
R. H. Qi4ct5ni'aV
Prin^Tipal Investigator
Publication of this report does not constitute Air Force approval of

the report's findings or conclusions. It is published only for the exchange
and stimulation of ideas.
W. H. Ebelke. Colonel, USAF

Chief, Propellant Division
•
AFRPL-TR-68-9
ABSTRACT
Work was continued on the study of Telagen S prepolymers for con-

ventional and advanced propellant systems. The factors affecting low
temperature behavior of conventional systems and a replacement for CTI
received most attention this quarter. Saturation of Telagen prepolymers
definitely causes poor low temperature properties in binders and propellants.
This was established by studies with a series of related polymers differing
only in saturation. Mixtures of saturated and unsaturated prepolymers were
not as good as a partially saturated prepolymer for low temperature behavior.
Prepolymer molecular weight and the nature of the crosslinker had very little
effect on the low temperature mechanical properties. Telagen S prepolymers
have been characterized by chromatography on silica gel. The Esso technique
has been simplified and an infrared method was used to follow the function-
ality of the eluted polymer. Preparative chromatography to obtain di-
functional prepolymer for binder and propellant studies was developed. Aging
studies were continued and aging of binders with partially saturated pre-
polymers was begun.
The study of advanced systems was continued by model compound and

propellant investigations using HDP and KAP. Acetylazetidine and 2,5-di-
oxaspiroj_3,3j heptane were incompatible with HAP and only the latter was
compatible with HDP. However the dioxaspiroheptane did not react with
acid at 50°C. It was observed that HA? and HDP very rapidly dehydrate
secondary alcohols. With these materials only primary alcohols may be
used. Some HAP propellants were made.
AFRPL-TR-68-9
TABLE OF CONTENTS
Page
I. INTRODUCTION 1
II. OBJECTIVE 1
III. SUMMARY 1
IV. TECHNICAL DISCUSSION 3
A. Task One 3
1. Introduction 3
2. New Prepolymers 3
3. Characterization of Ingredients Li
ij. Chromatographie Studies 5
5. Prepolymer Functionality 11
6. Low Temperature Properties 12
7. Replacement of CTI 2d
B. Task Two 32
1. Introduction 32
2. Model Studies }?.
3. KAP Propellants bl
h. HDP Propellant 12
C. Task Three h2
1. Introduction L2
2. Preparation of 1-Acetylazetidine Ii2
D. Task Four hit
1. Introduction Uh
2. Effect of Prepolyîer '",•. uration on -inder Aginr hi
3. At:ing of Conventional Propellants Lij
AFRPL-TR-68-9
LIST OF TABLES
Number Page
I Properties of Some Telagen S Prepolymers 3
II Fractionation of Telagen S 7
III Relation of Relative Intensities of Infrared Bands 9

to Mono- and Di- Functionality for Prepolymer 15ÖH
IV Preparative Chromatography of Prepolymer l£8H 9
V Practical Functionality of Telagen S Prepolymers 12
VI Composition and Properties of Telagen S Binders 13
VII Effect of Mixtures of Unsaturated and Saturated 20

Prepolymers on Low Temperature Behavior of Binders
VTII Compositions and Properties of Propellants Prepared 2k

with Telagen S Prepolymers
IX Compositions and Properties of Telagen S Propellants 26

Crosslinked with GTRO
X Relation of Crosslink Density and Mechanical 29

Behavior of Hydrocarbon Binders
XI Extent of Reaction of Dioxaspiroheptane (1.75N) and 33

Propionic Acid (1.75N) in the Presence of KAP and HDP
(8o|£) After 18 Hours in Benzene
XII Reaction of 2-0ctanol (0.88N) with n-1-Decenylsuccinic }h

Anhydride (0.88N) in the Presence of HAP and HDP (80*)
at 23°C in Benzene
XIII Reaction of 2-0ctanol (0.88N) with n-1-Decenylsuccinic 37

Anhydride (0.88N) in the Presence of HDP (8(A) at 23 C
and Ethyl fJ-Phenylcarbamate in Benzene
XIV Reaction of 1-Octanol (0.88N) with n-1-Decenylsuccinic 38

Anhydride (0.88K) in the Presence ol HDP (60S) at 23°C
in Benzene
ii
AFRPL-TR-68-9
LIST OF TABI£S
(Cont)
Number
XV Reaction of 2-Ethylhexanol (0.88N) with n-1- Decenyl- 36

succinic Anhydride (0.88N) in the Presence of HDP (8c$)
at 23°C in Benzene
XVI Reaction of 2-Ethylhexanol (0.8ÖN) with n-Dodecylsuccinic 39

Anhydride (0.88N) in the Presence of HDP (W) at 23°C
in Benzene
XVII Reaction of 1-üctanol (0.88M) with n-1-Decenylsuccinic 29

Anhydride (0.88N) in the Presence of HDP (8c#) at 23°C
in Benzene
XVIII Reaction of 2-Ethylhexanol (0.88N) with n-1-Decenyl- hO

succinic Anhydride (0.88N) in the Presence of HDP
(30%) at 23°C in Benzene
XIX Reaction of 1-Octanol (0.88N) with Dodecylsuccinic hO

Anhydride (0.88N) in the Presence of HDP (80$) at
23°C in Benzene
XX Mechanical Behavior of Telagen S and Minuteraan Wing VI US
Second Stage PropeHants at -75°F and 10C# Relative
Humidity in Carbon Dioxide Environment
XXI Mechanical Properties of Telagen S and Minuteman lj6
Wing VI Second Stage Propellants at 0°F and 100$
Relative Humidity in Carbon Dioxide Environment
XXIT Mechanical Properties of Telagen S and Minuteman hi

Wing VI Second Stage Propellants at 77°F and 5% Relative
Humidity in Stagnant Argon Environment
XXIII Mechanical Properties of Telagen S and Minuteman 18

Wing VI Second Stage Propellants at 77°F and $OjL
Relative Humidity in Stagnant Argon Environment
XXIV Mechanical Properties of Telagen S and Minuteman h®

Wing VI Second Stage Propellants at 77°F and 25*
Relative Humidity in Circulating Air Environment
iii
<,
AFRPL-TR-68-9
LIST OF TABLES
(Cont)
Number Page
XXV Mechanical Properties of Telagen S and Minuteman 50

Wing VI Second Stage Propellants at 77°F and 5<#
XXVI Mechanical Properties of Telagen S and Minuteman 51

Wing VI Second Stage Propellants at 77°F and 8(#
Relative Humidity in Stagnant Air Environment
XXVII Mechanical Properties of Telagen S and Minuteman 52

Wing VI Second Stage Propellants at 1,'0°F and 2%
XXVIII Mechanical Properties of Telagen S and Minuteman 53

Wing VI Second Stage Propellants at 170°F and 8(#
Relative Humidity in Stagnant Air Environment
iv
AFRPL-TR-63-9
LIST OF FIGURES
Number Page
1 Chromatographie Fractionation or Prepolymer 6
lljöAH on SiO
2 Chromatographie Fractionation of Telagen S on SiCL 8
3 Infrared Spectrum of Fractionated Prepolymer 158H 10

h Effect of Mixtures of onsaturated and Saturated 19
Prepolymers on Low Temperature Behavior of Binders
5 Relative Increase of Some Mechanical Properties of 22

Telagen S Binders Between 4j0° and 77°F vs.
Saturation of Prepolymers
6 Effect of Crosslink Density on Binder Tensile Strength 30

7 Effect of Crosslink Density on Binder Modulus 31
8 Chromatocrams of the Reaction of 2-0ctanol with 35
n-1-Decenylsuccinic Anhydride in the Presence of
HDP at 23 C
9 Infrared Spectrum of Material Isolated by GLC 36
10 Infrared Spectrum of l-Acetylazetidine in .lethylene k}

Chloride
otos..:.\•tY
c1 nnd c2 l •r>tmr:,y- 1?i vlln Con::Jtnnt:;

C-1 ~:,I. -rii- ~ 2 -r.yanoethyl ) -2, J·1ih,ydroxyprOJ')Y'lll'Ylinc
Carwinate H-125 i1 •lt 1 -Dii:Jocyann tndiphenyL"'lethano, product of 'h~
u~ john Co1:1pany
CTI .di.socyanate, pr"vrictary itttm of the
At~r·>Jt:.lL-
••moral Corporation
DDI ll.,lO U.t:-a~ryl ~iisocyannt~
derived frorn J·:mttry DiiT•t:r Acid,
product uf General :-tills, Inc.
Eo Initial uniaxial modulus

E-2L6 ~Jull,iJ'WlCtional isocy~mata, product or ;!obay
Ches•Ll.c a .J. {, or.tpa ny
FeAA l·'Ul'rl~ DC'ltylacctou:.t.o
OI.C Gas-llqu.i d chrotna t r·r~raphy

OTRO :1l,'f(~cro1 t riricinolcn t.e
HAA Acetvlnr. t.one
HDI
IDP lall.lccyl p13largonn l.•l, product o!' 'frr.~ry

Indnstl'ios, Inc.
meq/gm ··:Ll UequivDl•mto per gram

mm/gm liilli~ol~..!S per ;:rorn
NHR. Uuclcur li\ll~notic resonance
Oronite 6 .L.• 1uid pol,yioobut·f, ,m•, prnrluct or t.h~ CalU·ornia
Cht.z•tical Compan 1
PAPI Pol,'fphenyl pol,yJ.:1ocyaruate, product of the CrR
0)v\~ion, Upjohn Company
vi
AFRPL-TR-68-9
GLOSSARY (cont)
Polycin 23 Diol, product of Baker Castor Oil Company
Polycin $1 Diol, product of Baker Castor Oil Company
Telagen Functionally-terminated polybutadiene, product of

The General Tire and Rubber Company
Telagen S Functionally-terminated hydrogenated polybutadiene,

product of the General Tire & Rubber Company
TiO(AA) Titanyl acetylacetonate

'2
TM? Trimethylolpropane
VPO Vapor phase osmometer
Uniaxial strain at break

%
r Maximum uniaxial strain
m
Uniaxial break stress
"b
rr Uniaxial maximum stress
ra
vii
•
BLANK PAG
AFRPL-TR-63-9
TIE DEVELOPMENT AND EVALUATION OF A HYDROCARBON BINDER

FOR HIGH KNERGY SOLID PROPELLANTS
I. INTRODUCTION
This is the seventh Quarterly Technical Report submitted in partial

fulfillment of the requirements of Contract AF Qli (6ll) -IÜ419 • The report
covers the period lij September through 13 December 1°67.
II. OBJECTIVE
The objective of this program is to further develop and evaluate a

solid propellant binder system specifically to meet the most rigid demands
of advanced, high performance solid rocket motors, fhe solid propellant
binder system consists of an isocyanate-cured, saturated hydrocarbon pre-
polymer developed and evaluated under Contract AF Qlj(6ll)-10336. Further
development and evaluation will involve propellant optimization, testing
of curatives for room temperature cures, replacing CT1, attaining batter
low temperature properties, determining the effect of burning rate modifiers,
adaptation to advanced fuels and oxidizers, formulations containing both
advanced fuels and oxidizers, and a study of environmental stability.
III. SU.1HARY
A. A series of three prepolymers made from the sajne polybutadiene

were obtained from The General Tire and Rubber Company. These prepolymers
were from 0 to 93$ saturated. 1 hey were characterized anil the results are
reported.
B. A pilot plant batch of CTI was made. The yield was 55% of
material with an equivalent weight of 72.3 (theoretical, 69.0). The iso-
cyanate, Carwinate 12$M was purified by crystallization of a hexane soluble
fraction. This purification technique did not succeed with Mobay E-2li6.
C. Small and large scale Chromatographie fractionations of Telagen S

have been made. The technique is a simplified variation of that developed
by workers at the Esso Research & Engineering Company and involves the use
of three solvents for small scale characterization studies and a single
solvent for large scale preparative studies. The characterization studies
have been in general agreement with the Esso work. The preparative work is
designed to isolate difunctional material for preparation of propellant.
-1-
(
' •
D. A novel method for following functionality changes during

chromatography of Telagen S was developed. The functionality of the eluted
polymer is estimated from the ratios of the intensities of the OH band at
3330 cm"1 to CH bands at 13Ö0 and H16O cm"1.
E. The effect of saturation on the low temperature behavior of

Telagen S binders has been determined from a series of related prepolymers.
The results confirm the previous conclusion that saturation is the single
most pronounced effect tending to give poor low temperature behavior. While
the use of mixtures of a saturated and an unsaturated prepolymer gives some
improvement of low temperature mechanical properties, the mixture is not as
effective as a partially saturated prepolymer of equivalent olefin content.
F. The mechanical properties at low temperature differ very little

for binders made with unsaturated and 60$ saturated prepolymer. The low
temperature behavior changes radically at saturations between 60 and 9(#.
The effect of prepolymer molecular weight is very slight. No effect of
crosslinkers on low temperature properties was observed for binders cross-
linked with GTRO, E-2I16, and PAPI.
G. Generally the conclusions regarding the effects of saturation,

prepolymer molecular weight, and crosslinkers have been substantiated by
propellant studies.
H. GTRO, Mobay E-2q6, and PAPI were studied as replacements for

CTI and all are considered good prospects. Binders crosslinked with GTRO
give properties which are not highly dependent upon the crosslink densities.
I. Actylazetidine was incompatible with HAP. The azetidine was

consumed with no loss of the co-reactant, propionic acid. The oxetane,
2,$-diosaspiro [3,3] heptane, was compatible with HDP but not with HAP. The
oxetane and acid did not react at 50 C.
J. The reactions of 1-octanol and of 2-ethylhexanol with n-1-

decenylsuccinic anhydride were too rapid and the method used could not
determine which alcohol reacts faster. Similarly the rates of n-1-decenyl-
succinic and dodecylsuccinic anhydrides with 1-cctanol could not be
distinguished by the method used because the rates were too rapid.
K. Model compound studies of HDP or HAP propellants show that

secondary hydroxy terminated alcohols, in stirred or mixed composites, were
dehydrated very rapidly (faster than about 8^/min.). The dehydration rate
was markedly higher with HDP.
L. Advanced propellant studies with primary hydroxy terminated

prepolymers indicated that Oronite 6 is better than IDP as plasticizer and
that GTRO is better than TMP as crosslinker. A cure catalyst is not required,
M. Aging studies on binders made with prepolymers of different

saturation have begun. No data are available.
-2-
IV. TECHNICAL DISCUSSION
A. TASK ONE
1. Introduction
Task One involves prepolymer characterization, improved

low temperature properties, curing agent substitutes for CTI, the effects
of plasticizer and burning rate modifiers, room temperature curing and
boron-workhorse binder systems. A propellant designed for low temperature
capability, a propellant cured at room temperature, and a propellant with
a CTI replacement will be prepared for long-term aging.
2. New Prepolymers
The General Tire and Rubber Company has submitted an

unsaturated prepolymer and two partially saturated ones derived from it.
The prepolymers and some of their properties are listed in Table I.
Table I
PROPERTIES OF SOME TEUGEN S PRFPOLYMERS
Lot No. 2ij2AM-l69 3HPL-123 3HPL-12

Molecular Weight (VPO) 1600 - -
Equivalent height 1080 1130 1150

Hydroxyl Content, meq/gm 0.928 O.683 0.872
Unsaturation, mn/gm 17 6 1
1,2-vinyl, % )b 6.Ö 0
l,lj-trans, % 28 - -
l,ij-cis, % 38 - -
Brookfield Viscosity, 3o •95 325

pcises at 25°C
-3-
3. Characterization of Ingredients
a. New Prepolymers
The degree of saturation of prepolymers recently-

received from The General Tire and Rubber Company was determined by combi-
nation of NMR to determine total protons on olefinic groups and IR to
determine total vinyl groups. The results, assuming the unhydrogenated
polybutadiene to be 100$ unsaturated, are: 2lj2AM-l69, 100$ unsaturated;
3HPL-123, 39,6% unsaturated; 3HPL-125, 7.2$ unsaturated. The corresponding
values determined by The General Tire and Rubber Company b.ve 100, 35.3, and
5.9%'y agreement is satisfactory for the intended experiments.
b. CTI
A large batch of CTI was made in pilot plant equip-

ment with a SS% yield based on 15 lb of starting material. The equivalent
weight of the product was 72.3 (theoretical, 69.0). An earlier batch in
pilot plant equipment had given a very low yield. The present run demonstrates
the successful scale up of CTI preparation.
c. Carwinate 12$M
Impure Carwinate 125M (h,h '-Diisocyanatodiphenyl-

methane), equivalent weight of lhS, was refluxed with hexane. The yellow
crystals, which separated, from the cooled hexane, had a melting point
30-31°C and an equivalent weight of 126 (theoretical 125).
d. Mobay E-2h6
Mobay E-2lj6, a multifunctional aromatic isocyanate

(functionality, 2.69), is a dark liquid. The successful purification of
the Carwinate 125M encouraged an attempt to purify E-2l»6. The purification
was not successful.
E-2li6 is very soluble in benzene, toluene, dichloro-
methane, chloroform, and carbon tetrachloride, is moderately soluble in
cyclohexane, and very slightly soluble in hexane, heptane, and p-xylene.
The E-2lj6 was extracted with cyclohexane and with hexane, but in both cases
the infrared spectrum of the soluble portion was similar to that of the
original. There was no difference in the equivalent weights determined by
the dibutylamine method.
e. Functionality of DDI-liilO and GTRO

VPO molecular weight studies of DDI-llilO and GTRO
used in experiments described in this report were made. The molecular
weight of DDI-llilO was 608. Its functionality was 2.06 based on an experi-
mentally determined equivalent weight of 295. The GTRO had a molecular
-h-
1
weight of 903 (theoretical molecular weight of 932) and an equivalent

weight of 3JLi2 which corresponds to a functionality of 2.6h.
b. Chromatographie Studies
a. Experimental
The successful fractionation of Prepolymer liiÖAH

into non-, mono-, and difunctional components by workers at the Esso Research
and Engineering Company^ encouraged further experiment along these lines.
The complex solvent system used by these workers was simplified and applied
to several prepolymers, the objective being to determine the non- and mono-
functional contents of the prepolymers.
Two grams of II48AH were introduced into a 7/8" diameter

column packed with 100g of 100-200 mesh silica gel in CCljj. CCl^, CHCI3, and
CH2CI2 (1200 ml of each) were used to elute the material from the column and
20-ml fractions were collected by an automatic fraction collector. The
solvent was evaporated and an elution profile constructed. The results,
similar to those reported by Esso, showed three distinctly separate major
fractions. About 30$ of -one material is non-functional and monofunctional.
A duplicate run was made to check these results. While the duplicate showed
some differer es with respect to retention times, the fractions and their
quantities were similar to those obtained in the first experiment. The
elution profiles are illustrated in Figure 1.
An infrared spectrum of each of the three major

fractions was run in a semi-quantitative method to determine their functional
group content. The first fraction (approximately 10Ü? of the total) showed
very low OH absorption and the second fraction (approximately 2C# of the
total) showed a higher OH absorption which, however, was lc-er than that of
the third fraction.
The above procedure was also applied to fractionate

prepolymers 158H and 161AHR. The results with I6IAHR were almost identical
to these with 15>8H except for the percentage of material comprising each of
the three major fractions. With 161AHR, the first fraction contained approx-
imately 13% of the total material, and the second fraction contained an
additional 17$.
* B. E. Hudson and A. H. Muenker, "Functionality Determination of Binder

Prepolymers", Ksso Research and Engineering Company, Quarterly Progress
Report"3, GR-3-FBP-67, 1 April to 30 June 1967- Contract No. FOij6ill-67-
C-0012.
-5-
CHROMATOGRAPHIC FRACTIONATION OF PREPOLYMER 148AH
ON Si02
•-10*-!
50
V^^^J '"vl
1
' ' ' ' i ' ' i i
0 500 1000 1500 2000
Elution Volume, ml
-6-
Figure 1
The results of both 158H and l6lAHR compare very
closely with those found for II48AH. The elution profiles are shown in
Figure 2 and the data are summarized in Table II. The size of Fraction III
did not correlate with the functionality derived from curing studies. Thus
the functionality of Prepolymer 1I18AH was judged to be higher than that of
158H or I6IAHR which were approximately similar. The calculated function-
alities of these prepolymers, eliminating the nonfunctional Fraction I and
assuming non-recovered material as part of difunctional Fraction III, are:
llj8AH, 1.78; l58H, 1.82; and 161AHR, 1.80.
Table II
FRACTIONATION OF TELAGEM S
Compositi Dn, wt% of original

Prepolymer Fraction
Lot No. I n ni^
Ü4ÖAH 10 20 70
158H 12 15 73
I6IAHR 13 17 70
Material not recovered from the column (about 10£ for

llj8AH and 1$SH) included.
b. Preparative
An effort was made to separate enough of the

difunctional Fraction III to prepare propellants. The column used was
four feet in length and three inches in diameter. Five pounds of silica
gel (100-200 mesh) were slurried with chloroform and placed in the column
giving a three foot bed. Fifty grams of Prepolymer 15ÖH were diluted to
50£ with chloroform and added to the column. The progress of the elution
was followed by infrared spectroscopy. The intensity of the CH band at
29ii0 cm~l showed the amount of prepolymer passing through the column. The
non- and monofunctional prepolymers were eluted after sixteen fractions,
each 500 ml of CHClo collected at 1 liter per hour. Fractions 1 to 11,
after evaporation 01 the solvent, showed no CH band at 3330 cm"*, but
Fractions 12 to 16 showed OH absorption.
CHROMATOGRAPH IC FRACTIONATION OF
TRAGEN S ON SiO,
Prepolymer 158H
Elution Volume, ml
Figure 2
The functionalities of the fractions were determined
from the ratios of intensities of the hydroxyl band (3330 cm"-*-) to those of
the CH bands at lij60 cm"1 and 1380 cm-1. Prepolymer 158H (functionality,
1.68) was the standard from which the relative intensities to be expected
for a given functionality of the fractions were determined (Table III).
Table III
RELATION OF REIATIVE INTENSITIES OF INFRARED BANDS

TO MONO- AND DI- FUNCTIONALITY FOR PREPOLYMER 158H
Expected Relative Intensities

Functionality 3330/lTO 3330/1380
1 0.212 0.M16
2 0.lj25 0.89:
The CH band at 29hC cm" could also have been used for this determination,
but it is so intense relative to the OH band that two solutions of proper
concentration would have been required for the Perkin-Elmer laboratory
instrument used for this study.
Table IV indicates the results and the infrared

spectrum of Fraction 18 which is the difunctional fraction is shown in
Figure 3.
Table IV
PREPARATIVE CHROMATOGRAPHY OF ^POLYMER 153H
Fraction Weight Weight

No. Percent Functionality
1 to 8 fa.l 8.2 0
9 to 11 7.9 15.8 0
12 to Ub 5.9 11.8 0.75
15 to 16 li.l 0.2 0.99
17a 11.7 23.Ii 1.1b
I8b 9.li 18.8 2.55c
Recovery hl.l 86.2
uHCl, fraction just preceding acetone flush
Acetone-water flush
c
Valua on undried sample
-9-
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-10- Figure 3
The large scale separations are continuing to obtain
50 to 100g of prepolymer of functionality close to two. Subsequently this
material will be used to prepare propeilant. The results of the large
scale separations do not match exactly those obtained in the smaller scale
ones, but the purpose of the large scale work is to separate large quantities
(in a relative sense) of material of higher functionality. To achieve this
purpose, some fractionation efficiency is sacrificed for speed and quantity.
5. Prepolymer Functionality
The inadequacy of using functionality as determined from

the ratio of molecular weight to equivalent weight ratio to formulate
propeilant binders ha? been frequently pointed out during this program. A
typical example is Prepolymer l68H with a functionality of I.63 as determined
by the molecular weight to equivalent weight ratio. Such a polymer should
require an HDI to CTI equivalents ratio of 2.25 for incipient crosslinking.
In reality binders with a crosslink density of about 1 x 10*5 moles of
chains per cubic centimeter have been made at an HDI to CTI ratio of 6.0.
It is not known whether this situation arises from a higher actual function-
ality of the prepolymer, entanglements formed on curing, or crosslinks
introduced by side reactions, but this fact is an experimental reality.
To cope with this situation, the idea of "practical"

functionality was introduced. Practical functionality was calculated from
a cured binder whose crosslink density was known by the relation
(f.-2)W./E.f.I where XQ = crosslink density in moles of branch
points per gram, f^ • functionality of a binder component, W- = weight

fraction of a binder component, E. = equivalent weight of a binder component,
and the sum taken over all n reacting components (plasticizer is excluded
since it is not reacted). The equation has these limitations: it assumes
100:1 reaction during polymerization and is valid only where the branch point
has a functionality of 3. With the isocyanate system the extent of reaction
is very hip;h and the branch points can be kept to a functionality of 3.
The crosslink density has been determined from the

Mooney-Rivlin Cn constant, from the gel fraction, from the compression
modulus of a swollen binder and from the uniaxial equilibrium modulus of
a binder. All of these yield consistent values for the practical function-
ality from binders with wide range of HDI to CTI ratios. Table V lists the
functionalities by the molecular weight to equivalent weicht ratio and
practical functionalities for a number of prepolymers used in this program.
-11-
Table V
PRACTICAL FUNCTIONALITY OF TELAGEN S PREPOLYMERS
CTI/HDI at Functionality
No. of
Prepolymer
xD=o Data Practical M.W./E.W.
8507-1 -h 7.1 -0.119 3 2.01 1.71

2ij2AM-lij8Ab -0.0Ü4 6 2.00 1.70
2<J2AM-11J8AH 0.0611 20 1.98 1.62
2lj2AH-l58H 0.0136 11 1.92 1.68
2b2AM-l6lAHR 0.191 8 1.91 l.h9

2ij2AM-l68H 0.0662 7 1.96 1.63
CTI to HDI equivalents ratio required for incipient crosslinking. A

negative value indicates prepolymer can crosslink without a crosslinking
agent.
Unsaturated precursor of Prepolymer II48AH.
6. Low Temperature Properties
a. Introduction
T
:/ork done during the previous quarter (see Report
AFRPL-TR-67-260) indicated that the single most important factor influencing
the low temperature behavior of saturated binders was the degree of satura-
tion. The work of this quarter continued to confirm and to extend this
finding and to apply it to propellant studies. The effect of several curing
agents was shown to be negligible as far as low temperature behavior is
concerned.
b. Binder Studies
(1) General
The binders prepared and their properties are

summarized in Table VI. This table also includes binders made in the
-12-
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previous quarter, the complete property data for which have become avail-
able. For assessing the low temperature behavior of binders, the criterion
has been the ratio of a mechanical property such as break tensile, initial
modulus, or C^ at -hO°F to that at 77°F. The lower this ratio the better
will be the low temperature properties of a binder and hence, of a propellant.
Previous work has indicated that over the temperature range 1$0° to -75°F
propellant moduli are fifty times the corresponding binder moduli.
(2) Effect of Saturation
During the previous quarter, the very significant

influence of saturation on low temperature properties was indicated. This
work was not conclusive because the prepolymer molecixlar weight was not
controlled. The work of the previous quarter was confirmed with a series
of prepolymers of the same molecular weight ranging in saturation from 0 to
9$. The conclusion that saturation of functionally terminated polybutadienes
adversely affects low temperature behavior of binders made from these materials
was firmly established.
A series of binders (212-217) with varying ratios

of unsaturated (U48A) and saturated (ilj8AH) prepolymers were prepared to
compare such compositions with that prepared from a partially hydrogenated
prepolymer such as 3HPL-90. The C^ and gel fraction data indicate binders
of approximately equal crosslink density. In general, the properties at
77°F are similar. At -JjO°F, better elongation and lower moduli were obtained
with those compositions wherein the concentration of the unsaturated pre-
polymer was higher than that of the saturated. None of the compositions had
as low an increase in modulus from 77° to -l40°F as Binder 193 (3 fold) which
was prepared from the partially hydrogenated Prepolymer 3HPL-90. The vari-
ation of the change in properties as the temperature is decreased from 77°F
to -l40°F is indicated in Table VII and in Figure l|. The conclusion is drawn
that a mixture of saturated and unsaturated prepolymers is not as effective
as a partially saturated one for attaining low temperature properties.
Further studies were made with three prepolymers

of equal molecular weight and varying saturation. These prepolymers have
nearly the same equivalent weight since two of them, 3HPL-123 (60j£ saturated)
and 3HPL-125 (93$ saturated), were derived by hydrogenation of the third,
2lj2AM-l69 (unsaturated). The previously characterized prepolymer, 3HPL-90
(SM saturated), having twice the equivalent weight was used to prepare
controls for the evaluation. The HDI to CTI equivalents ratios were varied
within each series to obtain a range of crosslink densities. The binders
were swelled with toluene to obtain gel fractions. Crosslink densities
were calculated for several binders from compression moduli of the swelled
networks. Aging studies have been initiated to determine the oxidative
stability of these binders prepared from partially saturated prepolymers.
-18-
c
o
^5
TO
CO
<D
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"tj
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o R a 2
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-19-
Figure 4
Table VII
EFfECT OF MIXTURES OF UNSATURATED AND SATURATED PREPOLYMERS

ON LOW TEMPERATURE BEHAVIOR OF BINDERS8
Ratic> of Mech.
Reference Saturated to Effective Pre)p. at
No. Prepolymers Unsaturated Eq. Ratio Saturation % I4O0 to 77°F
E C.
212R HJ8A 0 0 11 7 2
213 HJ8A/11J8AH 0.25 20 I5b 12 5
21li HJ8A/HJ8AH 0.67 38 lib 9 9
215 HJ8A/11J8AH 1.50 57 21 18 u
216 HJ8A/HJ8AH b.o 76 ?9 2h 29

211 U48AH &o 95 2kb 20 111
2l42 3HPL-90C - % 5 5 8
composition of binders given in Table VI.

These values for doubtful because of tab failures at -qO°F testing.
Partially saturated prepolymer.
The mechanical properties of the cured binders

listed in Table VT reflect the differences in the degree of saturation of the
new prepolymers. The tensile strengths, moduli and C^ values of the binders
containing the unsaturated prepolymer 2lj2AM-l69 (Binders 25l to 251) increased
3 to Hi fold from 77° to 4iO°F. These values were slightly lower than those
obtained with Binders 239R to 2lj2R containing the 55$ saturated Prepolymer
3HPL-90 which has over twice the equivalent weight. Binders 2hl to 250 con-
taining the 6<# saturated Prepolymer 3HPL-123 gave tensile strength and C\
values increases averaging about 11 fold, moduli increases were higher. The
very low modulus values of these 30ft bars may have resulted in measurement
errors giving rise to the abnormally hiph modulus increase. The tensile
increase did not differ greatly from those for Binders 251 to 25b. Increase
-20-
•
of moduli, tensile strengths and CT values (ignoring that for Binder 2kl)
for Binders 2U3 to 2li6 prepared with the 93% saturated Prepolymer 3HPL-125)
averaged about 50 fold indicating inferior low temperature behavior. The
results indicate that the low temperature properties can be improved by-
using a prepolymer with about 60$ saturation. This can be seen more graph-
ically in Figure $.
The mechanical properties change very little for

0 to 6(# saturation, but the subsequent changes are more pronounced. The
final choice of a prepolymer will, however, require a knowledge of variation
of oxidative stability with saturation. These experiments are in progress.
(3) Effect of Prepolymer Molecular Weight
An original postulate for the poor low temperature

behavior of saturated binders was that the relatively low molecular weight of
the saturated prepolymers resulted in high polar group concentrations and that
these groups associated at low temperature. Data supported this postulate
(see Report AFRPL-TR-67-260) but not unambiguously. No effort to clear this
ambiguity was made because the effect, if it existed or not, was overshadowed
by the very pronounced effect of saturation on the low temperature properties.
However comparison of binders made from 3HPL-90 ($k% saturated, molecular
weight li200) with those made from 3HPL-123 (60# saturated, molecular weight
1630) indicate better low temperature properties with the higher molecular
weight prepolymer. Thus for Binders 239 to 2lj2R made with Prepolymer 3HPL-90
the ratios of properties at -I4O0 to those at 77°F are: n , 8j EQ, 7j and
Ci, 15 while for Binders 2hl to 2!?0 made with Prepolymer 3HPL-123, the ratios
are: CT, 11; EQ, IJOJ and C,, 11.
This means that since a less saturated prepolymer

has a lower viscosity, the prepolymer can be made to a higher molecular
weight than those of the current saturated prepolymers. As a result there
will be an improvement in propellant properties not only because of the
greater unsatur3tion but also because of the greater molecular weight.
(h) Effect of Crosslinker or curing Agents
Variation of the crosslinker or curing agent did

not greatly affect low temperature properties. This is discussed more
completely in Section IV.A.7.
c. Propellant Studies
(1) General
One-pound batches of propellants having binders

crosslinked with polyisocyanates or with glycerol triricinoleate (GTRO)
-21-
<
on
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-22-
Figure 5
were prepared for evaluation of low temperature properties. In the poly-
isocyanate cured system, diisocyanate DDI-HjlO (General Mills) and hexa-
methylene diisocyanate (HDI), were used as chain extenders, and these
systems were crosslinked with CTI or PAPI. The compositions and properties
of the propellants are given in Table VIII. DDI and HDI were used in the
systems crosslinked with GIRO (Table DC).
(2) Polyisocyanate Systems
(a) Effect of Unsaturation
Better low temperature mechanical properties

were very evident for propellants made with the partially saturated prepolymer
3HPL-90 (Batches 3689, 3^90, Ij3b7, U}h&). Mixtures of saturated and unsaturated
prepolymers (llj8AH and l2j8A, Batch 3691) had better low temperature mechanical
behavior than completely unsaturated systems, but the magnitude of the improve-
ment was not great. While comparisons involving Prepolymers 3HPL-90 with II18A
or AH must take into account the differences in molecular weight (ql60 for
3HPL-90 and 1750 for UJ8A), the molecular weight exerted only a minor influence
on the low temperature behavior of saturated binder propellants.
(b) Effect of Prepolymer Molecular Weight
The properties of Batches IGP-2888 and 28Ö6R,

which indicate the good reproducibility of these propellants, were compared
with those of Batch IGP-qlOOj the former were prepared with a saturated pre-
polymer of 990 molecular weight, the latter, with a saturated prepolymer of
178o molecular weight. There was no significant difference in mechanical
properties between the two propellant formulations at ambient or at -75°F.
The binder studies indicated only slight, if any, improvement of mechanical
properties could be expected by this increase of prepolymer molecular weight.
Further increase of molecular weight of a saturated prepolymer is not con-
sistent with low viscosity and good processability.
(c) Effect of Isocyanate Type
Comparison of Batches lilOO and ijl02 indicated

that the use of the relatively long chain diisocyanate, DDI-lljlO, did .lot
improve low temperature properties. This was shown by the increase in -75°
to 77°F moduli ratio (76 for the propellant with HDI and lb8 for that with
DDI).
PAPI might be a suitable substitute for CTI

as indicated by the data for Batches 3689, 3^90, and LlOO. The low tempera-
ture properties and the moduli ratio at -75° to 77°P were the sane for a
given prepolymer, and PAPI cured propellants showed only slightly inferior
properties at ambient temperatures. The greater elongation obtained by use
of PAPI was probably due to the lower moduli of propellants containing this
isocyanate.
-23-
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All propellants contained 88/6 solids, 3% IDP (except for I0P-iilO3), C-l,
HAA, and FeAA and were cured at 135°P for 7 days.
I1 if teen-second readings.
c~
Pre polymers at 1 to 1 equivalence ratio.
d
lM IDP.
-25-
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-26-
(d) Effect of Flatftieizer Concentration
Data from Batch b!03, v*hich contained 1.8$

IDP instead of JjL, were interesting. Although the properties at 77°F showed
the propellant to be relatively soft (low modulus and hardness), the low
temperature properties are very poor, and the ratio of moduli at -75° to
77°F is very high (2l|8). These results seemingly support the contention
that IDP helps achieve better low temperature properties.
(3) GTRO Crosslinked Systems
(a) General
Binder studies indicated that GTRO might

serve as a suitable low cost substitute for CTI. The data in Table IX
strongly support this conclusion and suggest further investigation of the
GTRO crosslinked systems.
(b) Effect of Unsaturation
Significantly better low temperature properties

are attained with the partially saturated prepolymer, 3HPL--50, than with the
saturated prepolymer, UJ8AH (compare Batch 3835 with 3837 and 3838 with 39hh).
The best balance of properties was obtained with 3HPL-90, GTRO and HDI ^Batch
3837). The low temperature properties of these propellants may be even
further improved by decreasing the ambient modulus of the propellants to
about 1J50.
(c) Effect of Isocyanate Type
As with the polyisocyanate crosslinked

systems, the use of DJI was disadvantageous (Compare Batch 3835 with 39hk
and 3837 with 3838), compared to HDI. Since the functionality of DDI-liilO
is 2.O6, the difficulty may be a low extont of reaction. Better elongation
at maximum stress (R ) and lower ratio of moduli at -75° to 77°F were obtained
with HDI. Partial substitution of a polyisocyanate (PAPI) for triol was
deleterious (Batch 39b6).
(d) Effect of Crosslink Ratio
An attempt to decrease the modulus and

crosslinK density of the propellant by increasing the prepolymer to GTRO
ratio caused only a minor change of the ambient modulus (compare Batch 3837
with h3h9)» The reason for this small change is not known at present and
requires further investigation.
-27-
(e) Effect of Pendant Ethyl Groups
Batch 3836 was prepared with a saturated

prepolymer containing a high concentration (66%) of pendant ethyl groups.
High ratio of moduli at -75° to 77°F and poor overall mechanical properties
were obtained.
7. Replacement of CTI
During this quarter more emphasis was plact,-d on the testing

of substitutes for CTI. Much of this work was coupled with the study of low
temperature properties and was reported in previous sections of this report.
The substitutes were tested in binders and propellants so that the data are
reported in Tables VI, VIII, and IX. Glycerin triricinoleate, E-2ij6, and
PAPT were considered as substitutes.
Binders were prepared to evaluate GTRO as a crosslinking

agent for Telagen binders. Two diisocyanates, hexamethylene diisocyanate
(HDI) and DDI-lblO (dimeryl diisocyanate; General Mills) were used. Two
diols, Polycin 23 and 51 from Baker Castor Oil Co., were also evaluated as
co-diols. Since difficulty was encountered in obtaining consistent cures
with a 1 to 1 NCO to OH ratio, a 1.05 ratio was used in most of the formu-
lations .
The data in Table VI show that a significantly lower cross-

link density is obtained with DDI-lijlO than with HDI (compare Binders 21ÖA
with 219A, 22b with 225, 226 with 228, and 232 with 233). This results in
higher elongations and lower moduli. These results were confirmed in
propellant studies (Table IX). Compare Fropellant 3637 with 3838 or 3Ö35
with 39b b.
Another interesting aspect of the use of GTRO is revealed

in the data in Table X and the Figures 6 and 7 which show the relation
between the uniaxiaL maximum ( «•- break) tensile strength and initial modulus
and crosslink density. The Binders 211 to 235 made with Prepolymer llj8AH
and GTRO do not have properties - crosslink relation shown by the Binders
239 to 25b, all of which were crosslinked by isocyanates. The GTRO-cross-
linked binders have almost no dependence upon crosslink density.
It xs unlikely that this is due to Prepolymer lijÖAH because

the properties of Prupolymer 3HPL-125 which is 9}% saturated vary with the
crosslink density and the properties of CTI-crosslinked binders of Pre-
polymer II48AH have been shown to be dependent upon the crosslink density of
the binder (Figures II and 12, R ^01 *t *FRFL-TR-67-J.5o). The effect may be
related to the high NCO to OH ratio (1.05) used to cure these binders.
Binders crosslinked w.th E-2b6 (No. 255) or PAPI (Nos. 257, 258 and 260)
have properties which depend upon the crosslink density.
-28-
•
Table X
REIATION OF CROSSLINK DENSITY AND MECHANICAL BEHAVIOR

OF HYDROCARBON BINDERS
Mechanical
Properties
Crosslink Density at 77UF
n e
Ref. No. Prepolymer Crosslinker 10 moles chain/cc m m E
psi T psi
211 U48AH CTI 1.07 17 198 17
218A H48AH GTRO 0.88 16 353 16
22b H48AH GTRO 0.67 17 b52 10
225 lb8AH GTRO 1.02 lb 265 11
226 H18AH GTRO 1.87 17 226 20
235 lb8AH GTRO 2.6 20 115 32
239 3HPL-90 CTI 0.1b 7 716 6

239R 3HPL-90 CTI 0.32 18 712 17
2liO 3HPL-90 CTI 0.31 17 720 15
2b OR 3HPL-90 CTI 0.36 22 720 17
21.1 3HPL-90 CTI 0.22 13 711 Hi
2b IR 3HPL-90 CTI O.bl 23 713 19
2ij2 3HPL-90 CTI 0.50 26 69b 19
2b 2R 3HPL-90 CTI O.bO 11 716 7
255 3HPL-90 E-2b6 0.30 10 523 13
257 3HPL-90 PAPI 0.21 10 719 9
258 3HPL-90 PAPI 0.05 2 711 6
260 3HPL-90 GTRO/PAPI 0.19 9 720 10
2b 3 3HPL-125 CTI 0.15 6 705 10

2bb 3HPL-125 CTI 0.2b 9 709 7
2b5 3HPL-125 CT"r 0.23 8 706 6
2b6 3HPL-125 CTI O.bb 19 708 2
2b 7 3HPL-123 CTI 0.13 5 707 2

2b 8 3HPL-123 CTI 0.10 3 765 2
219 3HPL-123 CTI 0.26 10 705 3
250 3HPL-123 CTI 0.35 9 500 2
251 I69 CTI 0.18 7 706 6

252 I69 CTI 0.32 12 b80 6
253 169 CTI 0.30 \1 571 *-*
25b 169 CTI O.bO 12 b50 8
-29-
EFFECT OF CROSSLINK DENSITY ON BINDER TENSILE STRENGTH
/ r
p
JA (
0 0 • ~"o~
p
al
10
to
Prepolymer
0 148 AH
i G
A
3 HPL-90
3HPI-1?5
r o -;HI3L-123
O 169
i
0 1.0 2.0 3.0
Crosslink Density, 10^ moles of chain/o:
-30- Figure 6
.
EFFECT OF CROSSLINK DENSITY ON BINDER MODULUS
10
Prepolymer
O 148 AH
G 3HPL-90
A 3HPL-125
^> O 3HPL-123
O 169
1 -
1.0 5 2.0 3.0
Crosslink Density, 10 moles chain/cc
-31- Figure 7
B. TASK TWO
1. Introduction
Task Two involves the determination of the compatibility

of the prepolymers and curing agents with combinations of advanced oxidizer
and advanced fu.ii. Model compounds are being used to study the binder com-
ponent interactions with the fuels and oxidizers, and attempts are being
made to improve systems which have poor compatibility. Compatible systems
will be evaluated ballistically at the 1-lb scale,
2. Model Studies
• i. Introduction
The compatibility and reactivity studies reported here

were done with model compounds to simul te various functional characteristics
of prepolymers and curing agents. Thesi; model compounds could be readily
analyzed or identified by gas-liquid chromatography and by infrared analysis.
In general these studies were made in benzene to simulate the non-polar nature
of the hydrocarbon polymer chain and at concentrations typical for propellant
system. An internal standard was included to calibrate the detector response.
b. 1-Acetylazetidine
The compatibility cf 1-acetylazetidine in benzene with

HAP and the reaction of the azetidine with propionic acid also in benzene in
•'"..he presence of this oxidizer were studied. The gas Chromatographie data
indicated that acetylazetidine is not compatible with HAP. The azetidine
disappeared from solution immediately. Since the solution of HAP neutralized
with saturated aqueous potassium bicarbonate did not regenerate the azetidine
in the benzene phase, the azetidine reacted with HAP rather than being
adsorbed. After 2 clays at 23°C and 50°C, there was no loss of propionic acid.
c. 2,5-Dioxaspiro[3,3J heptane
The compatibility of the oxetane, dioxaspiroheptane
with HAP and HDP and its reaction with propionic acid in the presence of HAP
and HDP were studied. Gas Chromatographie data of the reactions are shown
in Table XT.
The oxetane showed poor compatibility with HAP but

good stability in the presence of HEP. The reaction of the oxetane with
propionic acid in the presence of HAP and HDP did not occur under the
reaction conditions studied. A catalyst or change in the oxetane structure
may promote the reaction between oxetane and acid in the presence of HDP.
This work is not presently being pursued.
-32-
.
Table XI
EXTENT OF REACTION OF DIOXASPIROHEPTANE (1.75N) AND

PROPIONIC ACID (1.75N) IN THE PRESENCE OF
HAP AND HDP (805C) AFTER 18 HOURS IN BENZENE
Amount Remaining,
Vlt.Jg of Original
Qxidizer Temp., °C Propionic Acid Oxetane
HAP 23 - 6h
23 100 liO
50 - 0
50 97 0
HDP 23 - 90
23 100 92
50 - 82
50 100 88
d. Reaction of Alcohols with Anhydrides in the

Presence cf Advanced Oxidizers
The reaction of 2-octanol with n-1-decenylsuccinic

anhydride in the presence of HAP and HDP did not follow the anticipated
reaction path. Instead of the alcohol reacting with the anhydride, the
alcohol was dehydrated to form 2-octene. The octene was isolated in a
refrigerated multiple internal reflectance cell as it passed from the
Chromatograph (Figure 8), and identified from its infrared spectrum
(Figure 9). The rate data in Table XII indicate that the alcohol was con-
sumed and the alkene was formed at the same rate. Presumably, the anhydride
loss was due to reaction with water formed from the dehydration of the
alcohol. The dehydration of ethanol by HAP has been reported by workers
at the Midwest Research Institute.'*'
7=n
vx;
A. D. McElroy and J. W. Nebgen, "Studies of Stability Problems in
Advanced Propellants", Midwest Research Institute, Quarterly Progress
Report No. 3, 1 April - 30 June 1967, 21 July 1967, Contract F0h6ll-67-
C-0022 (Confidential).
-33-
Table XII
REACTION OF 2-OCTANOL (0.88N) WITH n-1-DECENYLSUCCINIC

ANHYDRIDE (0.88N) IN THE PRESENCE OF HAP AND HDP (8$)
AT 23°C IN BENZENE
Concentration, Wt.% Original

Time,
Solid Minutes 2-0ctenea 2-Octanol Anhydride
HDP 0 0 100 100
15 h2 50 77.5
37 61 37 69
55 67 32 62
108 30 19 57
HAP 0 0 100 100
10 12.5 85 88.5
20 - 82 -
30 2luli Ih 86
5o 30.7 - -
90 lil.8 60 67
150 51.2 n.s 69
% of original octanol.
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Figure 9
m
A weak base, ethyl N-phenylcarbamate (1 to 1 equiva-
lents ratio to HDP), was added to the reaction solution to decrease the
acidic nature e* HDP. The data in Table XIII show that addition of the
carbamate had no effect on the reaction. That the carbamate was neither
adsorbed by nor reacted with HDP was demonstrated by the following. A
sample of HDP was titrated with 0.1N KOH in methanol to a phenolphthalein
end point. The titration values for three samples made up in molar ratios
of 0.5, 1.0, and 1.5 ethyl N-phenylcarbamate to HDP were the same as that
of the control without carbamate indicating that no reaction or adsorption
had taken place. This point was further demonstrated by tne fact that, as
indicated by gas chromatography, the ethyl N-phenylcarbamate concentration
did not change as the reaction progressed between decenylsuccinic anhydride
and octanol in the presence of HDP.
Table XIII
REACTION OF 2-0CTAN0L (0.88N) WITH n-1-DECENYLSUCCINIC

ANHYDRIDE (0.88N) IN THE PRESENCE OF HDP (8o£) AT 23°C
AND ETHYL N-PHENYLCARBAMATE IN BENZENE
Concentration, Wt.% of Original

Time,
Minutes 2-0ctenea 2-Octanol Carbamate Anhydride
10 17.5 Sh 91 85.5
30 19 50 96 88.5
90 68.5 26.7 87 77.0
135 81.1 17.8 9h
% of original octanol.
on the oiher hand, the reaction of i-octanol with

n-1-decenyl-succinic anhydride apparently gave the expected ester but at
too r^pid a rate to be of use as a propellant cure system (Tarle XIV).
The octanol was consumed somewhat more rapidly than the anhydride. This
was not due to dehydration, because the octene peal: was not observed on the
chromatogram., A possible reaction is that of octanol with the acid group of
an anhydride which has already undergone ring opening.
-37-
Table XIV
REACTION OF 1-OCTANOL (0.88N) WITH n-1-DECENYLSUCCINIC

ANHYDRIDE (0.88N) IN THE PRESENCE OF HDP (8(#)
AT 23°C IN BENZENE
Amount lemaining,
vJt.% of Original
Time
Minutes 1-Octanol Anhydride
15 3b.6 5b.2
35 20.7 I4O.I4
60 15.8 314.6
120 9.2 33.2
2-Ethylhexanol was substituted for 1-octanol to slow

the rate of the anhydride alcohol reaction. The rate increased instead of
decreasing (Table XV). A change of the anhydride from n-1-decenyl
(unsaturated) to dodecylsuccinic slowed the rate to that observed with
1-octanol indicating that the conjugated double bond increases the reactivity
of the anhydride (Table XVI).
Table 3t V
REACTION OF 2-ETHYLHEXANOL (0.88N) WEH n~l-DECENYI£UCCINIC

ANHYDRIDE (O.88N) IN THE FHBSENC3 OF HDP (8C#)
AT 23°C IN BENZEW5
Compound Remaining
Wt.jS of Original
i une, —- ' ~ "
Minutes 2-Ethylhexanol Anhydride
10 26 bO
30 8.9 27.8
60 8.3 26.I4
-38-
Table XVI
REACTION OF 2-ETHYLH2XAN0L (0.88N) WITH n-DODECYLSUCCINIC

ANHYDRIDE (0.88N) IN THE PRESENCE OF HDP (8(#)
AT 23°C IN BENZENE
Compound Remaining,
\it,% of Original
Time,
Minutes Alcohol Anhydride
15 hO.3 L2.6
ho 22.2 22 ,k
90 15.2 18,,6
Repeat experiments (Tables XVII an.! XVIII) indicated

that the reactions were too rapid to establish accurately which reaction
was faster. The reaction of 1-octanol with dcdecylsuccinic anhydride was
studied to compare it with the reaction of 1-octanol with the corresponding
unsaturated compound, n-1-decenylsuccinic anhydride« The cata in Table XIX
compared with previous data indicate that these reactions were also too
rapid to establish accurately which reaction was faster.
Table XVII
REACTION OF 1-0CTAN0L (0.88N) WITH n-1-DECENYLSUCCINIC

ANHYDRIDE (0.88N) IN THE PRESENCE OF HDP (8C#)
AT 23°C IN BENZENE
Compoi ind Remaining,

wt",-' of Original
Time,
Minutes 1-OctanoL Anhydride
2 21.2 31.5
20 - 28.2
b5 lb. 9 25.L
60 UJ.7 20.6
-39-
Table XVIII
REACTION OF 2-ETHYLHEXANOL (0.88N) WITH n-1-DECENYLSUCCINIC

ANHYDRIDE (0.88N) IN THE PRESENCE OF HDP (8$)
AT 23°C IN BENZENE
Compound Remaining,
Wt.£ of Original
Time,
Minutes Alcohol Anhydride
2 27.0 142.7
20 13.2 32.6
h$ — 25.2
60 9.3 21.7
90 8.9 21. h
Table XIX
REACTION OF l-OCTANOL (O.88N) WITH DODECYLSUCCINIC

ANHYDRIDE (O.88N) IN THE PRESENCE OF HDP (8C#)
AT 23°C IN BENZENE
Compound Remaining,
Wt.< of Original
Time,
Minutes i-Octanol Anhydride
2 28.2 30.1i
25 17.1 20.5
120 Ifa.O 18.5
Further studies on the dehydration of 2-octanol to

2-octene in benzene solution and in the presence of HDP, indicated that
a stirred solution gave complete dehydration after 30 seconds of reactior
at room temperature. A similar test with HAP indicated a h percent con-
version to alkene after 30 seconds. In view of these facts, further propel-
lant formulations for the advanced oxidizers will utilize other approaches;
-10-
including the use of alcohols and prepolymers terminated with primary
hydroxyl groups rather than secondary hydroxyl groups to minimize the
dehydration side reaction and loss of functionality. The observation of
the dehydration reaction is significant for the future development of
isocyanate cured HDP or HAP propellants.
3. HAP Propellants
A one-pound batch of HAP propellant was made using the

isocyanate, Carwinate 125M, in an effort to improve mechanical properties.
The propellant became firm, but very little, if any, crosslinking occurred,
There were no si^ns of incompatibility or HAP degradation. The oxidizer
used for the batch was impure HAP which had been recrystallized, but was
probably still not as pure or as dry as it could have been.
The recrystallized HAP was further purified by a process

U3ed to make spheroidal particles. Two £0-gram batches were made with the
spheroidal HAP at different crosslink levels using Carwinate 12$M. These
batches cured in three days. The extent of cure was not as complete as
has been previously obtained using HAP which was known to be pure.
Ten gram propellant batches were made using prepolymer

with primary hydroxyl groups. Two HAP propellants were made using primary
hydroxyl prepolymer (l68H), TMP and Carwinate 12S>M. One was plasticized
with IDP; the other, with Oronite 6. Each of these batches was divided in
half. One-half was cured at lj0°C and the other, at 70°C.
Samples cured at high temperature turned green and gelled

within four hours. The samples cured at the lower temperature gelled over-
night. The low temperature IDP sanple had turned green but the Oronite 6
sample remained at the original grey color. None of these propellants was
satisfactory, but the Oronite 6 sample which was cured at low temperature
(ljO°C) was the best.
Another series of three 10-gram HA? propellants was made

using Oronite 6 and a 1JO°C cure temperature. Both Carwinate 125-1 and TMP
which are solid at room temperature and insoluble in the prepolymer, were
finely ground by a mortar and pestle prior to dispensing.
The first two batches were made with Prepolymer 168H, TKP
(80 to ?0 equivalents ratio of 168H to TMP), and Carwinate 125M and the
third was made with GTRO in place of TMP (prepolymer to GTRO ratio, 6o/ljO).
The TMP-crosslinked batches became very hare? ût showed little evidence of
crosslinking. The third batch with 60 to JjG equivalents ratio of 168H to
GTRO was well cured overnight and showed good resiliance. This propellant
was the best of this series.
-a-
A portion of each of the three propellants was catalyzed
with TiO(AA)2> but there was no difference between the catalyzed and
uncatalyzed portions.
h. HLP Propellant
A 10-gram batch of HDP propellant was made using hydroxy

terminated prepolymer, GTRO and Carwinate 125M. This propellant cured within
an hour. The following safety data was obtained.
Bureau of Mines Impact (5C# PT), cm/2kg 10g
Friction Sensitivity ($$ PT), 1000 gm load 5200 rpm
DTA - Onset of exotherm, °F 223

Exotherm peaks, °F 32li, 335, 3h&
Endotherm peak, °F 193
The systematic study of the chemistry of HAP and HDP

propellants will be continued and improvement s will be introduced until a
satisfactory advanced propellant has been formulated and tested.
C. TASK THREE
1, Introduction
The achievement of a room temperature cure and obtaining

a suitable replacement for CTI are the main studies for Task Three. The
synthesis of curing agents on an "as needed" basis is also being performed,
2. Preparation of 1-Acetyiazetidine
Into a 2-r.eck, 100-ml round-bottom flask fitted with a

dropping funnel, thermometer and magnetic stirrer and containing 30 ml of
water and 20 ml of methylene chloride were placed 2.6 grams of potassium
carbonate and 1.07 grams (0.019 moles) of acetyl chloride in 10 ml of
methylene chloride was added through a dropping funnel at a rate to main-
tain the temperature between 0 and 5CC. The reaction was stirred at 0°C
for one-half hour after completion of the addition.
The two phases of the reaction solution were separated.

The methylene chloride phase was washed twice with 10 ml of 2N aqueous
sodium hydroxide and then dried over 3 grams of sodium sulfate. After
removal of the methylene chloride, the crude yield was 0.53 grams (27^).
The material was of greater than 95% purity by gas chromatography. Identi-
fication was made by infrared spectrum, Figure 10.
-1,2-
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Figure 10
. D. TASK FOUR
1. Introduction
Task Four includes Phase Four (propeHants in aging before

March 196?) and also involves the aging of propellants prepared under Tasks
One and Two. It further includes ths testing at 350°C of selected Task One
propellants and the temperature cycling of propellants made with a CTI
replacement.
2
• Effect of Prepolymer Saturation on Binder Aging
Aging studies have been initiated to determine the effect

of oxidative crosslinking on binders prepared from prepolymers with various
degrees of unsaturation. The samples are being aged at 8o°C in a circulating
air atmosphere. The control samples are being a/*od in the same oven but are
sealed in ampules having an argon atmosphere. The samples will be studied
by a micro-swelling technique to determine the extent of oxidative effects.
No data are available for this report.
3. Aging of Conventional Propellants
In Tables XX to XXVIII, the aging data are presented for

conventional Telagen S propellants and Minuteman propellant stored as long
as 9 months. The new data do not alter the basic pattern. This pattern
is a pronounced deterioration caused by moisture expecially at higher
temperature. The unsaturated Minuteman propellant also shows oxidative
crosslinking which eventually increases the propellant modulus. The aging
is continuing.
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UNCLASSIFIED
Security Classification
DOCUMENT CONTROL DATA - R&D
(Security claaallication ol title, body ol abstract and indexing annotation mum' be entered when the overall report ia claaeltled)
! ORIGINATIN G ACTIVITY (Corporate authoT) * Za REPORT SECURITY C L ASSI FIC A TlON
Aerojet-General Corporation None

P. 0. Eox 158LJ7 2 6 GROUP
Sacramento. Gal i fnrni a

3 REPORT TITLE
THE DEVELOPMENT AND EVALUATION OF A HYDROCARBON FINDER

FOR HIGH ENERGY SOLID PROPELLANTS
4- DESCRIPTIVE NOTES (Type ol report and inclualv* Hat**)
Seventh Quarterly Report - Uj September - 13 December 196?

5 AUTHORfS; (Lmmt name, tint name. Initial)
Quacchia, Rodney H.
Di Milo, Anthony J.
6. REPORT DATE 7# TOTAL NO. OF PAGES 7fc NO. OF REFS
January 1968 53 2
8«. CONTRACT OR GRANT NO. $a ORIGINATOP S 'EPORT NUMBERfSj
AF 0li(6ll)-llbl9
b. PROJECT NO. JL030-82Q-7
3b 18
9b. OTHER REPORT N of 3/ (A ny other number» ih.l m*y k* «iilfnid
thla report)
10. AVAILABILITY/LIMITATION NOTICES

This document is subject to special export controls and each transmittal to
foreign Governments or foreign nationals may be made only with prior approval
of AFRPL (RPPR-STINFO), Edwards, California 93523
11. SUPPLEMENTARY NOTES 12 SPONSORING MILITARY ACTIVITY
Air Force Rocket Propulsion Laboratory

Research and Technology Operations
Edwards, California
13 ABSTRACT Air Force Systems Command
United States Air Force
Work was continued on the study of Telagen S prepolyriers for conventional-and
advanced propellant systems. The factors affecting low temperature behavior of
conventional systems and a replacement for CTI received most attention this quar-
ter. Saturation of Telagen prepolymers definitely causes poor low temperature
properties in binders and propeHants. This was established by studies with a
series of related polymers differing only in saturation. Mixtures of saturated
and unsaturated prepolymers were not as good as a partially saturated prepolymer
for low temperature behavior. Prepolymer molecular weight and the nature of the
crosslinker had very little effect on the low temperature mechanical properties.
Telagen S prepolymers have been simplified and an infrared method was used to
follow the functionality of the eluted polymer. Preparative chromatography to
obtain difunctional prepolymer for binder and propellant studies was developed.
Aging studies were continued and aging of binders with partially saturated pre-
polymers was begun.
The study of advanced cystens was continued by model compound and propellant
investigations using HDP and HAP. Acetylazetidine and 2,5-dioxaspiro[3,3] heptane
were incompatible with HAP and only the latter was compatible with HDP. However
the dioxaspiroheptane did not react with acid at 50°C. It was observed that HAP
and HDP very rapidly dehydrate secondary alcohols. With these materials only
primary alcohols may be used. Some HAP propeHants were made.
DD FORM
1 JAN «4 1473 TIC LASS TF UP
IJNCIASSFIED
14 LINK A LINK B LINK C
KEY WORDS
Saturated Hydrocarbon Binders

High Energy Solid Propellants
Telagen S
Characterization of Saturated Prepolymers
Low Temperature Behavior of Saturated Binders
and Propellants
Effect of Prepolymer Saturation on Low
Temperature Mechanical Properties
Silica Gel Chromatography of Telagen S
Compatibility Studies with HAP and HDP
Dehydration of Alcohols by HAP and HDP
Acid Anhydrides as Curing Agents
Aging of Hydrocarbon Propellants
INSTRUCTIONS
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UNCLASSIFIED

THIS PAGE IS UNCLASSIFIED

AFR PL-TR-68-9 AGC 1030-83l-7

Quarterly Technical Report AFRPL-TR-68-9

This document is subject to special export controla and each tranam1ttal to

al .aiOI ... "...................... ..

''When U.s • Government drav'...n1s, specifications, or other

THE DEVELOPMENT AND EVALUATION OF A HYDROOARBON BINDER

R. H. Quacchia and A. J. Di l1ilo

This dooumtnt is subject to special export controls and each transmittal

This technical report was prepared under Contract No. AF OL(611)-llL19

Solid Propellant iteseareh Section

Publication or this report does not constitute Air Force approval or

W. H. Ebelke, Colonel, USAF

\·lork wa~ continued on the study of Telagen S prepolymers for con-

"When U.S. Government drawings, specifications, or other

THE DEVELOPMENT AND EVALUATION OF A HYDROCARBON BINDER

R. H. Quacchia and A. J. Di Milo

This document is subject to special export controls and each transmittal

This technical report was prepared under Contract No. AF Oij(611)-III4I9

Acknowledgment is made to the following persons who have contributed

Prepared By: Approved By:

Publication of this report does not constitute Air Force approval of

W. H. Ebelke. Colonel, USAF

Work was continued on the study of Telagen S prepolymers for con-

The study of advanced systems was continued by model compound and

ij. Chromatographie Studies 5

6. Low Temperature Properties 12

2. Preparation of 1-Acetylazetidine Ii2

D. Task Four hit

I Properties of Some Telagen S Prepolymers 3

III Relation of Relative Intensities of Infrared Bands 9

IV Preparative Chromatography of Prepolymer l£8H 9

V Practical Functionality of Telagen S Prepolymers 12

VI Composition and Properties of Telagen S Binders 13

VII Effect of Mixtures of Unsaturated and Saturated 20

VTII Compositions and Properties of Propellants Prepared 2k

IX Compositions and Properties of Telagen S Propellants 26

X Relation of Crosslink Density and Mechanical 29

XI Extent of Reaction of Dioxaspiroheptane (1.75N) and 33

XII Reaction of 2-0ctanol (0.88N) with n-1-Decenylsuccinic }h

XIII Reaction of 2-0ctanol (0.88N) with n-1-Decenylsuccinic 37

XIV Reaction of 1-Octanol (0.88N) with n-1-Decenylsuccinic 38

XV Reaction of 2-Ethylhexanol (0.88N) with n-1- Decenyl- 36

XVI Reaction of 2-Ethylhexanol (0.8ÖN) with n-Dodecylsuccinic 39

XVII Reaction of 1-üctanol (0.88M) with n-1-Decenylsuccinic 29

XVIII Reaction of 2-Ethylhexanol (0.88N) with n-1-Decenyl- hO

XIX Reaction of 1-Octanol (0.88N) with Dodecylsuccinic hO

XXIT Mechanical Properties of Telagen S and Minuteman hi

XXIII Mechanical Properties of Telagen S and Minuteman 18

XXIV Mechanical Properties of Telagen S and Minuteman h®

XXV Mechanical Properties of Telagen S and Minuteman 50

XXVI Mechanical Properties of Telagen S and Minuteman 51

XXVII Mechanical Properties of Telagen S and Minuteman 52

XXVIII Mechanical Properties of Telagen S and Minuteman 53

3 Infrared Spectrum of Fractionated Prepolymer 158H 10

5 Relative Increase of Some Mechanical Properties of 22

6 Effect of Crosslink Density on Binder Tensile Strength 30

10 Infrared Spectrum of l-Acetylazetidine in .lethylene k}