Process for preparing polyamides of PACP

A process for preparing polyamides of 2,2-bis(4-aminocyclohexyl)-propane (PACP) or methyl derivatives thereof with a C.sub.8 to C.sub.12 straight chain alkane dicarboxylic acid, or mixture thereof with adipic acid, which comprises preparing a moderate molecular weight prepolymer of the diamine and diacid or diacid mixture employing a manganous hypophosphite/water catalyst system, and thereafter condensing the prepolymer to a high molecular weight product.

FIELD OF THE INVENTION 
The invention relates to polyamides of P or of its methyl derivatives 
with C.sub.8 to C.sub.12 dicarboxylic acids, optionally with adipic acid. 
In another aspect, the invention relates to a method of preparing 
polyamides of P or methyl derivatives thereof with C.sub.8 to C.sub.12 
dicarboxylic acids, optionally with adipic acid. 
BACKGROUND OF THE INVENTION 
It has been difficult to obtain polyamides of 
2,2-bis(4-aminocyclohexyl)propane (P) and its methyl derivatives with 
diacids possessing a really sufficiently high inherent viscosity. Progress 
toward making same has been generally unrewarding, or not sufficiently 
successful to provide a viable commercial product. Methods directed toward 
preparation of products with high inherent viscosity have resulted in 
products which cannot be extruded from conventional autoclaves after 
polymerization, and thus are exceedingly hard to recover from the 
preparatory equipment so as to be utilized in any reasonable fashion. 
The vast potentialities for polyamides of P and its methyl derivatives 
await a viable method of preparation of the polyamides. 
SUMMARY OF THE INVENTION 
I have discovered a process for making high molecular weight polymers of 
(A) P, or its methyl derivatives, with (B) at least one C.sub.8 to 
C.sub.12 straight chain alkane diacid, or mixture thereof with adipic 
acid, by a two stage process. A prepolymer of a moderate inherent 
viscosity is first formed using a novel catalyst system comprising 
manganous hypophosphite and water, followed by second-stage 
polycondensation of the prepolymer to a high molecular weight product with 
a high inherent viscosity.

DETAILED DESCRIPTION OF THE INVENTION 
In accordance with my invention, high molecular weight polymers of (A) P 
or its methyl derivatives with (B) alkane dicarboxylic acids are prepared 
in a two-stage polymerization. The process comprises preparation of a 
prepolymer of the diamine and diacid monomer or monomers employing a 
catalyst system comprising manganous hypophosphite and water. The 
prepolymer so-prepared has a sufficient residual polymerization capability 
so as to permit condensation polymerization to high molecular weight 
products. This finishing step or conversion step can optionally employ low 
levels of manganous hypophosphite. 
While I do not wish to be bound by theoretical considerations in view of my 
highly effective operable process which is convenient and easy to use, 
nevertheless it presently appears that the prepolymer product prepared 
between the diamine and diacid monomers employing the manganous 
hypophosphite/water catalyst system results in a moderate molecular weight 
(moderate inherent viscosity) prepolymer having a sufficient balance and 
number of residual, unreacted, acid and amine end-groups which permit 
condensation polymerization of this prepolymer to a high molecular weight 
product. 
Diamines 
The (A) diamine employed is P or its methyl derivatives, more 
particularly 2,2-bis(4-aminocyclohexyl)propane and its monomethyl and 
dimethyl derivatives, such that each ring is substituted with not more 
than one methyl group. The P or methyl derivatives thereof can be 
represented by the formula 
##STR1## 
wherein each R is selected from hydrogen and methyl radicals. Any of the 
geometric isomers can be employed as can mixtures of the diamines. 
Diacids 
The (B) diacids employed are the C.sub.8 to C.sub.12 straight chain alkane 
dicarboxylic acids, one or more or in admixture with the C.sub.6 diacid, 
adipic acid. Thus, the polymers prepared in accordance with my invention 
are polymers of (A) P or a methyl derivative thereof with either (B1) 
at least one C.sub.8 to C.sub.12 straight chain alkane dicarboxylic acid, 
or (B2) a mixture of hexanedioic acid (adipic acid) with at least one 
C.sub.8 to C.sub.12 straight chain dicarboxylic acid. The C.sub.8 to 
C.sub.12 dicarboxylic acids are octanedioic acid (suberic), nonanedioic 
acid (azelaic acid), decanedioic acid (sebacic acid), undecanedioic acid, 
and dodecanedioic acid, any of these alone, or two or more. 
According to my invention, there is provided a prepolymer prepared by 
reacting (A) P or a methyl derivative thereof with (B) at least one 
C.sub.8 to C.sub.12 straight chain alkane dicarboxylic acid, preferably 
the C.sub.9 diacid azelaic acid, or mixture thereof with adipic acid, 
employing a catalyst combination of manganous hypophosphite and water. 
When the mixture (B2) of acids is employed including adipic acid, the 
mixture preferably comprises about 20 to 65 mole percent adipic acid, with 
the balance selected from the higher straight chain alkane dicarboxylic 
acid or acids. 
In preparation of the prepolymer, the desired amounts and ratios of P or 
methyl derivative thereof with the selected one or more dicarboxylic acids 
are admixed together with manganous hypophosphite, and water, employing in 
the range of about 20 to 500 ppm manganous hypophosphite, Mn(H.sub.2 
PO.sub.2).sub.2, based on weight of total monomers charged, with a 
presently preferred range of about 50 to 250 ppm. The amount of water 
employed should be in the range of about 7 to 50 weight percent based on 
total monomers charged, with a presently preferred range of about 8 to 40, 
and presently most preferred about 9-30 weight percent. Optionally, if 
desired, a small amount of manganous hypophosphite can be admixed with the 
prepolymer prior to the second stage polycondensation in the range of 
about 10 to 250 ppm. 
The moles of diamine charged to the reactor to obtain the desired 
prepolymer presently preferably should be approximately equal to the total 
moles of diacid employed, i.e., a molar ratio of diamine:diacid of about 
1:1. However, suitable prepolymer can be prepared in systems employing 
from up to about 2.75 percent molar excess of diamine to about a 1.75 
percent molar excess of diacid (1.75 molar percent deficiency of diamine), 
presently preferred up to about 2.25 mole percent excess diamine to about 
1.25 mole percent excess diacid, and presently more preferred about 1.25 
mole percent excess diamine to about 1.25 mole percent excess diacid. It 
is presently considered that variations greater than these one way or the 
other do not produce suitable prepolymer, i.e., prepolymer suitable for 
further condensation polymerization to a high molecular weight product. 
In the first stage, the monomeric reactants and catalyst components are 
charged to a suitable reactor means, such as an autoclave, which 
preferably has been purged of air using a sweep of a reaction-inert gas 
such as nitrogen, and then subjected to prepolymerization under elevated 
temperature and pressures by raising the temperature in the reactor means 
from ambient temperatures to such as about 175.degree. to 245.degree. C.; 
employing a pressure in the range of such as about 60 to 250 psig; over a 
time of such as about 5 to 120 minutes; presently more preferably raising 
the temperature to about 205.degree.-215.degree. C. over a time interval 
of about 30 to 60 minutes. The reactants should be maintained at this 
elevated temperature and pressure for an additional time of such as about 
10 to 120 minutes, presently preferred about 15 to 75 minutes. 
The temperature of the reactants then is further increased to such as about 
280.degree. to 320.degree. C. over a period of such as about 15 to 120 
minutes, preferably to temperatures of about 300.degree. to 315.degree. C. 
over a time of about 30 to 90 minutes. During this period, the pressure is 
adjusted to such as about 110 to 500 psig, preferably about 350 to 450 
psig with venting, if necessary. 
When the reactants have reached the maximum pressure and temperature above 
described, the reactants should be held for a time of such as about 10 to 
120 minutes, presently preferred about 15 to 60 minutes. 
The pressure in the reaction means thereupon should be gradually reduced to 
such as about 200 to 50 psig over a suitable time of such as about 10 to 
60 minutes, preferably to about 150 to 75 psig over a time of about 20 to 
40 minutes, while holding the temperature at about the maximum reached 
previously. 
The reactants then should be held at this reduced pressure, while still 
maintaining the maximum temperature, for a time of such as about 10 to 60 
minutes, preferred about 20 to 40 minutes. 
Thereafter, the reactor means are vented down to 0 psig, employing a 
reasonable time as may be convenient to avoid foaming of the reaction 
mass, such as about 10 to 60 minutes, more usually about 20 to 40 minutes. 
Optionally, a nitrogen sweep step can be employed at this point, in order 
to remove all traces of water vapor to prevent polymer foaming. 
The so-prepared product then is recovered, such as by extrusion, 
conveniently employing a broad recovery time of about 0 to 30 minutes, 
presently preferred about 2 to 15 minutes. 
The following Table I summarizes the broad preferred and more preferred 
modes of preparing the prepolymer: 
TABLE I 
__________________________________________________________________________ 
PROCESS STEPS FOR STAGE ONE POLYAMIDE PREPOLYMER PRODUCTION 
Step 
Ranges Time (Minutes) 
Temperature, Pressure, psig 
__________________________________________________________________________ 
1 Broad Preferred 
5-120 room tempeature.fwdarw. 175-245 
60-250 
More Preferred 
30-60 room temperature.fwdarw. 205-215 
2 Broad 10-120 hold at maximum 
60-250 
Preferred 15-75 temperature of Step 1 
3 Broad 15-120 280-320 110-500 
Preferred 30-90 300-315 350-450 
4 Broad 10-120 held at maximum 
Pressure of Step 3 
Preferred 15-60 temperature of Step 3 
5 Broad 10-60 maximum Pressure of Step.fwdarw. 200-50 
Preferred 20-40 temperature of Step 3 
Pressure of Step 3.fwdarw. 150-75 
6 Broad 10-60 maximum 
Pressure of Step 5 
Preferred 20-40 temperature of Step 3 
7 Broad 10-60 maximum 
Vent to zero 
Preferred 20-40 temperature of Step 3 
8 Broad 0-30 maximum 
(Pre-polymer recovery) zero 
Preferred 2-15 temperature of Step 3 
__________________________________________________________________________ 
The product at this stage, which I consider the end of the first stage or 
prepolymerization stage, is termed a prepolymer and exhibits an inherent 
viscosity of about 0.6 to 0.95, most usually and preferably about 0.7 to 
0.85. A prepolymer with such an inherent viscosity exhibits a low enough 
melt viscosity to allow 80 to 85 percent product extrusion from the 
prepolymerization reactor means, and yet has sufficient melt strength and 
toughness to substantially eliminate handling problems in further steps. 
In the second stage of my process, the so-formed prepolymer is subjected to 
a further melt polymerization step employing temperatures in the range of 
about 250.degree. to 310.degree. C., presently preferred about 260.degree. 
to 290.degree. C., because in this temperature range the reaction rate is 
reasonably fast and thermal degradation of the polymer product is not. 
At least the final portion of the reaction period of the second step is 
conducted at pressures in the range of about 0.005 to 20 mm Hg, presently 
preferred about 0.01 to 0.5 mm Hg because this pressure range is readily 
obtained and the reaction rate is faster at reduced pressure. 
The second stage or polycondensation stage is carried out under an inert 
atmosphere, such as provided by nitrogen or one of the rare gases such as 
argon or the like. Residence times for the second stage can vary as 
desired, depending to some extent on temperature and pressure, as long as 
sufficient to produce a polymer of the desired inherent viscosity 
substantially higher than that of the prepolymer such as at least about 
0.2 I.V. units and in the range of such as about 1 to 1.8, preferably 
about 1.1 to 1.7, more particularly at least about 1.2 to 1.4, yet 
residence times should be short enough to avoid polymer decomposition. 
The second stage reaction time will vary depending on whether it is carried 
out batchwise such as in an autoclave or continuously such as in a 
devolatilization extruder. In continuous operations, residence times 
typically will vary from about 2 minutes to 60 minutes, more usually about 
6 minutes to 20 minutes. In batch operations, reaction times typically 
will vary from about 30 minutes to 300 minutes. At these residence times 
throughput is reasonably fast coupled with a decreased probability of 
thermal degradation of the product polymer. 
Thus, my first stage is substantially a melt polymerization employing 
elevated temperatures and pressures and a novel catalyst system, whereas 
the second stage wherein the prepolymer is further melt polymerized to a 
high inherent viscosity product can be characterized as an elevated 
temperature-low pressure polycondensation step. 
The polycondensation second stage can be carried out in any suitable 
apparatus capable of heating the prepolymer to the desired temperature, 
has means for removing water vapor and other volatiles, and has means for 
reducing the pressure of at least the final portion of the reaction 
interval to the desired level. Thus, conventional autoclaves can be used, 
but devolatilizing reactor-extruders are particularly effective. 
The prepolymer can be polycondensed, for example, in a continuous or 
discontinuous polymerization system incorporating a vented, devolatilizing 
extrusion zone. Pressure is employed to push heated prepolymer to a heated 
extruder, provided with at least one vacuum vent. The vent or vents 
provide passages wherein the atmospheric pressure is reduced. As the 
polymer in the heated extruder advances through the extrusion zone past 
the vent or vents, the reduced pressure areas allow evaporation of 
volatile components. Since the polycondensation is carried out as a one 
phase liquid procedure with a controlled polymerization rate, oxidation, 
gelation and degradation of the polymer is avoided. 
EXAMPLES 
The following examples are included to assist one skilled in the art to 
which the invention pertains. The particular components, relationships, 
ratios, temperatures, pressures, and the like, should be considered as 
illustrative of the scope of my invention, without needlessly limiting the 
reasonable scope thereof. Product compositions are indicated by notations 
such as P-9/6 (60/40) which indicates a polyamide of 
2,2-bis(4-aminocyclohexyl)propane (P) with a 60/40 molar ratio mixture 
of the C.sub.9 diacid (azelaic) and C.sub.6 diacid (adipic). 
EXAMPLE I 
To a 5-gallon, anchor stirred stainless steel autoclave was charged 3501 g 
(14.69 moles) of 2,2-bis(4-aminocyclohexyl)propane (P), 1658.3 g (8.82 
moles) azelaic acid, 858.2 g (5.87 moles) adipic acid, 1504 ml distilled 
water, 0.30 g (50 ppm) optical brightener, and 0.60 g (100 ppm) of 
manganous hypophosphite. The reactor was sealed and flushed with nitrogen 
by alternately pressuring the nitrogen and venting to zero psig several 
times. The stirrer was started (10 rpm), and the reactor was heated to 
210.degree. C. and maintained at this temperature for 30 minutes. The 
reactor temperature was increased to 310.degree. C. with venting, as 
necessary, to maintain no more than 400 psig. The reactor was held at 
310.degree. C. at 400 psig for 15 minutes, and then was vented slowly to 
100 psig over 30 minutes as the temperature was maintained at 310.degree. 
C. The reactor temperature was maintained at 310.degree. C. and 100 psig 
for 15 minutes before venting slowly to 0 psig over a period of 30 
minutes. At this point, a plug was removed from the bottom of the reactor 
and nitrogen pressure was applied to extrude the molten prepolymer through 
the bottom drain hole. The prepolymer was extruded into a water quench 
bath wherein it was pulled to strand it. The strands were coiled into a 
large lever-pac and air-dried overnight. 
The strands were clear and colorless except for a slight blue fluorescence 
in sunlight due to the optical brightener present. The prepolymer product 
had an inherent viscosity (I.V.) of 0.78 (0.5% m-cresol solution at 
30.degree. C.). End-group analysis showed 69 acid equivalents and 85 amine 
equivalents per 10.sup.6 g of polymer. 
This prepolymer product of Run 1 possessed a sufficient number and balance 
of residual, unreacted acid and amine end groups to allow further 
condensation polymerization to high molecular weight polyamide as shown in 
Examples II-IV. 
EXAMPLE II 
A blend of the prepolymer product from Example I with that from four 
analogous runs gave a representative sample of P-9/6 (60/40) prepolymer 
of I.V. 0.79 for finishing to a high molecular weight polyamide. 
A 6 g portion of the above P-9/6 (60/40) prepolymer sample of 0.79 I.V. 
was charged to a small laboratory glass reactor which was flushed with 
nitrogen by alternately evacuating and pressuring to 15-20 psig N.sub.2 
three times. A slow stream of nitrogen then was maintained through the 
reactor as it was heated from 150.degree. C. to 320.degree. C. during a 
period of 30 minutes. The reactor then was held at 320.degree. C. under 
N.sub.2 flush for 1 hour. The pressure then was reduced to 20 mm Hg and 
maintained at 320.degree. C. for 1 hour with a small N.sub.2 bleed through 
the reactor. The reactor was finally pressured to 0 psig with N.sub.2 and 
allowed to cool under a nitrogen flush. The reactor was broken to remove 
the polymer of this Run 2 which possessed an inherent viscosity of 1.20 
(0.5% m-cresol solution at 30.degree. C.). 
Run 2 illustrates the finishing step or second step of my inventive process 
to produce a high inherent viscosity product. 
EXAMPLE III 
A 120 g sample of a prepolymer P-9/6 (60/40) of I.V. 0.77 prepared as in 
Example I was placed in a 1-liter anchor-stirred (12 rpm) stainless steel 
autoclave. The reactor was flushed with nitrogen by alternately pressuring 
to 120 psig with N.sub.2 and venting to 0 psig a total of four times. The 
reactor then was heated from room temperature to 305.degree. C. over a 
period of 45 minutes under N.sub.2 flush and was maintained at 305.degree. 
C. for 30 minutes with N.sub.2 flush. The pressure then was reduced to 20 
mm Hg over a 30 minute period at 305.degree. C. and held at this 
temperature for 30 minutes with a slight N.sub.2 bleed through the 
reactor. The reactor was pressured to 120 psig N.sub.2, sealed, and cooled 
to room temperature. Stirring the reactor contents during cooling was 
continued for 30 minutes to wrap the viscous product around the stirrer 
shaft to facilitate product removal. After cooling overnight, the reactor 
was opened and the product of Run 3 P-9/6 (60/40) high molecular 
weight polyamide was removed by chipping. The polyamide exhibited an I.V. 
of 1.41 (0.5% m-cresol solution at 30.degree. C.). 
This Run 3 illustrates that the P-9/6 (60/40) prepolymer can be 
effectively finished to a high molecular weight (high inherent viscosity) 
polyamide. Again, use of laboratory apparatus resulted in inconvenience in 
the recovery of product material. 
EXAMPLE IV 
A sample of a P-9/6 (60/40) prepolymer of I.V. = 0.77 prepared as in 
Example I was melted under an inert atmosphere, and the melt was charged 
to a continuous devolatilization reactor (Baker-Perkins Poly-Con.RTM.R-100 
stainless steel reactor). At a pressure of 0.10 mm Hg, a temperature of 
279.degree. C., a residence time of 12.1 minutes, and a rotor speed of 21 
rpm, the product of Run 4 was extruded which exhibited an I.V. of 1.3. 
Run 4 demonstrated that a devolatilization reactor means is applicable and 
convenient for large-scale production of high I.V. material suitable for 
commercial applications. 
EXAMPLE V 
To a 1-liter stirred stainless steel autoclave were charged 118.1 g (0.495 
mole) 2,2-bis(4-aminocyclohexyl)propane (P), 55.94 g (0.297 mole) 
azelaic acid, 28.95 g (0.198 mole) adipic acid, 50.7 ml distilled water, 
and 0.02 g (100 ppm) manganous hypophosphite. The reaction was carried out 
in essentially the same manner as described in Example I. The resulting 
P-9/6 (60/40) prepolymer exhibited an inherent viscosity of 0.80. 
A 5 g sample of the prepolymer was weighed into a flask for conversion to 
high molecular weight polyamide. The system was alternately pressured with 
N.sub.2 and evacuated prior to thermal polymerization of the prepolymer 
under N.sub.2. The system was heated from 120.degree. C. to 320.degree. C. 
over a 30-minute period under N.sub.2 flush, and then maintained at 
320.degree. C. for 1 hour. The pressure of the system then was reduced to 
20 mm Hg and the temperature was held at 320.degree. C. The product of Run 
5 was colorless and possessed an inherent viscosity of 1.25. 
Run 5, when compared with Run 6 as shown in Table II below, demonstrates 
the necessity of using manganous hypophosphite in the first stage of my 
process in order to obtain a prepolymer suitable for further 
polycondensation to a high molecular weight. 
EXAMPLE VI 
The same charge and procedure was followed in this Example as described in 
Example V above, except for the omission of manganous hypophosphite. The 
polymeric product of Run 6 had an inherent viscosity of only 0.64, and the 
final product exhibited an inherent viscosity of only 0.88, the relatively 
minor increase obtained by the second stage condensation polymerization. 
Thus, the prepolymer prepared without the manganous hypophosphite was 
unsuitable for further condensation polymerization to result in a high 
molecular weight polyamide with a desired high I.V. The following Table II 
compares the runs directly: 
Table II 
______________________________________ 
Effect of Added Manganous Hypophosphite 
I.V. After 
Final Ther- 
Polymeric 
mal Polycon- 
Ex- Product densation 
Run ample Mn(H.sub.2 PO.sub.2).sub.2 
I.V.-Step a 
Step b 
______________________________________ 
5 - Inventive 
V 100 ppm 0.80 1.25 
6 - Control 
VI None 0.64 0.88 
______________________________________ 
As can be seen from these results, the product of the control Run 6 was not 
convertible to a high molecular weight polyamide. These runs again 
demonstrate the necessity of using manganous hypophosphite in the first 
stage of my process in order to obtain a prepolymer suitable for further 
polymerization to a high molecular weight. 
EXAMPLE VII 
To a 5-gallon, anchor-stirred stainless steel autoclave was charged 3,574 g 
(15 moles) P, 1,692.9 g (9 moles) azelaic acid, 876.11 g (6 moles) 
adipic acid, 0.6143 g (100 ppm) manganous hypophosphite Mn(H.sub.2 
PO.sub.2).sub.2, 0.3072 g (50 ppm) of a commercially available optical 
brightener OB-1 4,4'-bis(benzoxazole-2-yl)stilbene!, and 614 ml (10 
weight percent relative to the monomers) of distilled water. 
The reactor was sealed, and flushed with nitrogen by alternately pressuring 
with nitrogen and venting to 0 psig several times. The stirrer was started 
at a rate of about 10 rpm, and the reactor contents heated to about 
210.degree. C. and maintained at this temperature for about 30 minutes, at 
which time the pressure was about 70 psig. The reactor temperature was 
increased to 310.degree. C., the pressure increasing at the higher 
temperature to about 400 psig, at which temperature over a period of 15 
minutes venting was commenced sufficient to hold the pressure at about 100 
psig. After about 15 minutes, the pressure was gradually vented to 0 psig 
over an interval of about 1 hour. Material of this Run 7 was extruded from 
the reactor at about 100 psig employing nitrogen pressure, and the 
inherent viscosity of this prepolymer sample was about 0.66. 
In a comparison Run 8 made substantially the same way, but omitting the 
water, 3500 g (14.7 moles) P were admixed with 1657.8 g (8.8 moles) 
azelaic acid, 857.97 g (5.87 moles) adipic acid, 0.3007 g (50 ppm) of 
optical brightener (OB-1), and 0.6016 g (100 ppm) manganous hypophosphite, 
and added to a reactor. The reactor was flushed with nitrogen several 
times, and sealed under 20 psig nitrogen pressure. The contents were 
heated over about 1 hour to a temperature of about 600.degree. F. 
(315.degree. C.), the contents reaching a maximum pressure of about 60 to 
70 psig. When a temperature of 600.degree. F. (315.degree. C.) was 
reached, the contents thereupon were slowly vented over about 11/2 hours 
to reduce the pressure substantially down to 0 psig, at which time the 
contents were extruded rapidly at 100 psig using nitrogen pressure. The 
product of Run 8 had a yellow color and was quite brittle, so brittle even 
that it could not be handled adequately during extrusion. When the reactor 
head was removed, the material remaining inside was heterogeneous, 
indicating incomplete reaction. Some opaque white, powderlike material, 
some distinctly yellow material, and other varieties were observed, 
indicating that a variety of types of products had been produced, which 
was an undesirable aspect. 
Runs 7 and 8 demonstrate the necessity and importance of including water in 
the formation of the prepolymer. 
EXAMPLE VIII 
The following runs demonstrate the importance of monomer stoichiometry in 
prepolymer production. 
Run 9 utilized an equimolar mixture of diacids and diamine, and was carried 
out in the same manner as the run described in Example I with the 
following charge: 
3409 g (14.30 moles) of 2,2-bis(4-aminocyclohexyl)propane (P) 
1615 g (8.58 moles) of azelaic acid 
835.7 g (5.72 moles) of adipic acid 
0.2930 g (50 ppm) of 4,4'-bis(benzoxazole)-2-yl)stilbene 
0.5860 g (100 ppm) of manganous hypophosphite 
1465 ml of distilled water. 
Run 10 utilized a 1 molar percent excess of diacids, and was similarly 
carried out with the following charge to the reactor: 
3417 g (14.33 moles) of 2,2-bis(4-aminocyclohexyl)propane (P) 
1635 g (8.686 moles) of azelaic acid 
846 g (5.791 moles) of adipic acid 
0.2949 g (50 ppm) of 4,4'-bis(benzoxazole-2-yl)stilbene 
0.5898 g (100 ppm) of manganous hypophosphite 
1475 ml of distilled water. 
Run 11 utilized a 1 molar percent excess of diamine, and was similarly 
carried out with the following charge to the reactor: 
3474 g (14.57 moles) of 2,2-bis(4-aminocyclohexyl)propane (P) 
1629 g (8.657 moles) of azelaic acid 
843.2 g (5.771 moles) of adipic acid 
0.2973 g (50 ppm) of 4,4'-bis(benzoxazole-2-yl)stilbene 
0.5946 g (100 ppm) of manganous hypophosphite 
1487 ml of distilled water. 
The essential results of these Runs 9, 10, and 11 are shown in Table III 
below: 
Table III 
______________________________________ 
Monomer Stoichiometry in Prepolymer Production 
Inherent Viscosity 
Molar % Molar % Step A After Second Stage 
Run Excess Excess Pre- Polycondensation 
No. Diacids P polymer 
Step b 
______________________________________ 
9 None None 0.86 1.69 
(i.e., (i.e., 
Equimolar) 
Equimolar) 
10 1.0 0.80 1.20 
11 1.0 0.80 1.51 
______________________________________ 
The data in Table III show that a slight excess of either diacids or 
diamines can be used but that equimolar amounts of diacids and diamine 
gives best results. 
Polyamides prepared from 2,2-bis(4-aminocyclohexyl)propane and/or its 
methyl derivatives, with the high molecular weight straight chain alkane 
dicarboxylic acids, optionally further with adipic acid, as I have 
described, are useful in the production of engineering thermoplastics, as 
packaging materials, and the like. 
The polyamides of my invention prepared in accordance with my process can 
be blended with fillers, pigments, stabilizers, softeners, extenders, 
other polymers, a variety of fillers such as graphite, carbon black, 
titanium dioxide, carbon fibers, silica, asbestos, cotton floc, and the 
like, in the usual manner. 
The disclosure, including the data, has illustrated the value and 
effectiveness of my invention. The examples, the knowledge and background 
of the field of the invention and of general principles of chemistry and 
other applicable sciences, have formed the bases from which the broad 
descriptions of the invention including the ranges of conditions and 
generic conditions of operant components have been developed, and have 
formed the bases for my claims here appended.