Note: Descriptions are shown in the official language in which they were submitted.
POLYAMINES BY AMINATIONLOF POLY~INO
INITIATED POLYOXYALKjLENE GLYCOLS
(D#80,762-F)
BACXGROUND OF THE INVENTION
1. Field of the Inventio~
This invention relates to polyoxyalkylenepolyamines and
to a method for their preparation by amination of alkylene
oxide adducts o~ polyamine initiators. In another aspect,
this invention relat~s to the use o~ the polyoxyalkylene-
polyamines in RIM elastomers and epoxy castings and adhesives.
2. Prio~ Art
The amination of long alkoxylated alkyl chains terminated
by hydroxyl groups is well-known in the art.
U.S. Patent No. 3,654,370 to E.L. Yeakey teaches the
amination Or polyoxyalkylQne polyols to rorm the correspond-
ing amines by means of ammonia and hydrogen over a catalyst
prepared by the reduction of a mixture of the oxides Or nick-
el, copper and chromium. The amination i8 carried out at a
temperature of 150 to 275C and 500 to 5000 psig.
U.S. Patent No. 4,409,399 to H.E. Swift, et al., teaches
a catalyst rOr aminating aliphatic alcohols and aldehydes.
The unsupported catalyst comprise~ (1) copper oxide or copper
hydroxide and (2) nickel oxide or nickel hydroxide, and op-
tionally (3) an oxide or hydroxide of a Group IIA; e.g.,
magnesium, barium. The reaction is carried out at a tempera-
ture o~ 150 to 250C and 1 to 100 atm with continuous water
removal.
u.S~ Patent No. 3,390,184 to P.H. Mos~, et al., tQaches
a process for converting a secondary alcohol to a high-molecu-
lar weight primary amine by means of a hydrogenation-dehydro-
genation catalyst comprising at least one member selected from
the group consisting of the metals and oxides of nickel and
cobalt, together with copper and a metal oxide selected from
the group consisting of chromium oxlde, molybdenum oxide,
manganese oxide and thorium oxide. The reaction is carried
out at a temperature of 225 to 260C and pressurQ of 2000 to
lo 4000 psig, with ammonia as the aminating agent.
U.S. Patent No. 3,373,204 to R.A. Hales, et al., teaches
a catalytic process for producing secondary aMines from deriv-
atives of phenols, alcohols and amine~ containing S to 40
moles of ethylene oxide and propylene oxide. The catalyst is
Raney nickel and ammonia or primary alkylamines as the aminat-
ing agent. The reaction is carried out at 200 to 275C with
the evolution of water. Amines include lauryl amine, hexa-
decyl amine, octadecyl amine, rosin amine and fatty acid
amines.
U.S. patent No. 3,347,926 to J.D. Zech teaches a cataly-
tic process for aminating primary and secondary aliphatic
alcohols. The catalyst comprises a chromium-promoted Raney
nickel. The reaction is carried out at 150 to 275C with
ammonia, primary amines or secondary amines of 1 to 6 carbon
atoms. --
U.S. Patent No. 2,923,696 to X.E. Harwell, et al.,
teaches resinous compositions formed by the reaction of an
epoxy resin with a high-boiling amine product. The patent
further teaches hydrogenation catalysts employing copper,
nickel, cobalt and oxides thereof.
U.S. Patent No. 4,130,590 to Hobbs, et al., teaches the
production of long-chain unsaturated amines such as N-(alka-
dienyl)amines and saturated or hydrated derivatives thereof.
SUMMARY OF THE INVENTION
Th$s invention relates to polyoxyalkylenepolyamines of
the formula:
R~ CH3 1 ~ IR' IC~ ~R
~N-CHCH2 1 ( OCH2 CHl~OCH2 CH~OCH2 CHt~ N~
lS wherein a + b + c ~ 2 - 100 and R is:
R' CH3 CH3
- ~ CH2 CHO~CH2 CHOt;~CH2 CH - NH2
R' is sQlected from the group consisting of hydro-
:` 20 gen and the methyl or ethyl radical,
x ranges from 0 to about 10,
y ranges from 2 to about-100,
n is 0 or 1, and with th~ prov$so that when n is
0, then R' is the methyl or ethyl radical.
Preforably, the sum of x ~ y ranges from about 2 to 50 and R'
is the methyl radical. :
This invention also relates to polyoxyalkylenepolyamines
of the formula:
CH3 R
CH ~ OCH 2CH ~ ~(
R
CH3 /R
R - C ~ CH 2~0CH 2CH-~ e
CH3 /R
oCH~ OCH 2CH ~ N\
R
wherein R is:
R ' C H3 IC H3
- ( CH2 CHO~CH2 CHOt~CH2 CH-NH2
R' is selected ~rom the group consisting of hydro-
qen and the methyl or ethyl radical,
x ranges from 0 to about 10,
y ranges ~rom 2 to about 100,
z is 0 or 1,
the sum of d + e + f ranges from 3 to about 100, and
R" is selected from the group consisting of hydro-
gen and the methyl or ethyl radical. .-
Preferably, the sum of d + ~ + f ranges ~rom 10 to about 90,
the su~-o~ x + y ranges from 2 to about 50, and R" is the
methyl radlcal.
In another aspect, this invention relates to a process
for producing a polyoxyalkylenepolyamine which comprises:
68626-272
,, ,
(A) alkoxylating a polyamine selected from the group
consisting of (1) an alkylenediamine, (2) a polyoxyalkylenediamine,
and (3) a polyoxyalkylenetriamine to form the corresponding
polyamine polyoxyalkylene polyol having at least two terminal
groups of the structure:
X X '
N CH
X/
wherein X is a hydroxyl-terminated polyoxyalkylene group and X'
is the methyl radical and with the proviso that in one of the
terminal groups formed when an alkylenediamine is alkoxylated X'
is hydrogen and when X' is hydrogen, the oxyalkylene segment of
the polyoxyalkylene groups attached to the nitrogen atom bears a
pendant methyl or ethyl radical, and
(B) catalytically aminating the said polyol with
ammonia in the presence of hydrogen to form the polyoxyalkylene-
polyamine.
The polyamines of this invention are particularly
suited for reaction with isocyanates to manufacture articles by
a Reaction Injection Molding (RIM) process.
Reaction Injection Molding (RIM) is a technique for
the rapid mixing and molding of large, fast-curing urethane
parts. RIM polyurethane parts are used in a variety of exterior
body applications on automobiles where the light weight
contributes to energy conservation. RIM parts are generally made
by rapidly mixing active hydrogen-containing materials with
polyisocyanate and placing the mixture into a mold where reaction
proceeds. After reaction and demolding, the parts
may be subjected to an additional curing step which comprises
placing the parts in an oven, held at 250F or higher.
Surprisingly, it also ha~ been found that the polyoxy-
alkylenepolyamines o~ this invention are useful as curing
agents in forming clear epoxy castings and adhesives with
highly satisfactory physical properties. Such epoxy products
find application in the electr~cal and electronic fields.
DESCRIPTION OF THE PREF~RRED EMBODIMENTS
The polyamine polyoxyalkylene glycols are aminated as
set out in U.S. Patent No. 3,654,370 to E.L. Yeakey, which
describes the amination o~ polyoxyalkylene polyols to form the
corresponding amines. The amination i8 conducted in the pres-
ence of a catalyst preparQd from a mixture o~ the oxides of
nickel, copper and chromium and in the presence of ammonia and
hydrogen at 150 to 275C and about 500 to about 5000 psig.
It has been discovered that the polyamine polyoxyalkylene
glycols formed by alkoxylatinq the polyamine initiators can
be reductively aminated provided that the internal tertiary
nitrogens are sterically hindered. Hindrance o~ the tertiary
nitrogens stabilizes the molecule and thus prevents cleavage
at the tertiary nitrogens by the metallic catalyst.
In the instant invention, each o~ the internal tertiary
nitrogen atoms is hindered by a pendant alkyl group attached
to the-''¢'arbon atom ad~acent to the tertiary nitrogen and/or
by pendant alkyl qroups o~ the oxyalkylene groups directly
attached to the tertiary nitrogen. If the tertiary nitrogens
are not hinderQd, the polyether chains are cleaved at the
nitrogen atoms, yielding a variety o~ decomposition products
, ~ . .. . . ~ ~
rather than the desired polyoxyakylenepolyamine. It is shown
in a comparative example that if attack on the tertiary nitro-
gen atom is not hindered, the identical process conditions
yield a wide variety of degradation products. For example,
when a compound such as:
H
N-t~CH2CH20 ~ CH2~ 0)30 5 3
CH3
is aminated, migration of the methyl group and cleavage of the
chain at the nitrogen atom predominates.
Preferred starting materials, i.e., the polyamine ini-
tiators, include, for example, 1,2-propane diamine, polyoxy-
alkylenediamines guch as the JEFFAMINE~ D series as exempli-
fied by:
JEFFAMINEO D-230 having the ~ormula:
.: ICH 3 CH 3
H2N HCH~0CH2 H ) 2 . 6 NH2
JEFFAMINE~ D-400 having the formula:
CH3 CIH3
H2NlHCH~OCH2CHt5 6 NH2
~EF~AMINE D-2000 having the ~ormula:
CH3 CH3
H2NCHCH t OCH2CH)33 I NH2
polyoxyalkylenediamines such, as the JEFFAMINE~ ED ser-
ies, as exempli~ied by:
JEFFAMINE~ ED-6000 having the ~ormula:
IH IH IH
H2NfcH2orfH2co~s.ll~fcH2o~(~MIsx( D2c.~2o)s3~sl~cH2cH2
CH3 CH3 CH3
Hl H
I~CH CH ot tCH C0) ]~CH C-0 ~ CH C-NH
(MIXED) I 1H3 CH3
and polyoxyalkylenetriamines, such as the JEFFAMINE~ T series,
as exemplified by:
JEFFAMINE~ T-403 having the ~ormula:
CH~
CH2~ocH2cH~NH2
CH
CH3CH2CI-CH2~0CH2CH~-NH2
¦ CH3
CH2-~OCH2CH~-NH2
wherein the sum o~ g + h + f i~ about 5.3 and
JEFFAMINE T-5000 having the ~ormula:
H H
CH 20~CH2 ~CO~CH2 ~C-NH 2
H H
HCO ~ CH2 C~ CH2 C-NH2
CH3 CH3
H H
Cl~ O ~ CH2 1 0 Ih Cl~ 1 ~2
CH3 CH3 8
wnerein the sum of ~ + k + m is about 85.
All of the above JEFFAMINE~ polyoxyalkyleneamine products are
marketed by the Texaco Chemical Company, Houston, Texas.
The alkoxylation is carried out according to methods well
known in the art and described in the Examples. Useful alkyl-
ene oxides include ethylene oxide, propylene oxide, and butyl-
ene oxide, while the preferred oxide is propylene oxide.
The following examples, which illustrate the nature of
the instant invention, are not intended to be limitative.
~XAMPLE 1
PREPARATIO~ OF THE 6200 MOLECVLAR WEIGHT
PROPYLEN~ XI~ ApDUCT OF 1.2-PROPANEDIAMI~ IPDA)
Six pounds 1,2-PDA was charged into a five-gallon kettle.
The reactor was then purged with prepurified nitrogen. Propy-
lene oxide (19.75 lb) was then reacted at 100C at 50 psig.
Approximately one hour was requlred for addition Or the propy-
lene oxide. The reaction mixture was then digested at 120-
125~C, for one hour, vacuum strippQd to a minimum pressure,
nitrogen stripped, and drained from the kettle. Properties
of the tetrol intermediate, i.e., 1,2-propanediamine al~oxy-
lated with 4 moles of propylene oxide (PDA-4PO), were as
follows:
~ Total amine, meq/g 3.27
Tertiary amine, meq/g 3.27
Hydroxyl no., mg XOH/g 713
Water, wt% 0.03
pH in 10:6 isopropanol-water 11.6
Viscosity, 77~F, cps ~ 1.5 x 10'
Into a ten-gallon kettle were charged 10 lb of the PDA-
4PO and 151.2 g 45~ aguQous potassium hydroxide. The reactor
was then purged with prepuri~isd nitrogen. The initiator was
then dried to a water content o~ less than 0.1% using both
vacuum and nitrogen stripping. Propylene oxide (10 lb) was
reacted at 105-llO-C at 50 psig over a three-hour period.
After digestion to an equilibrlum pre~ure, the initiator was
neutralized at 95C by stirring two hours with 600 g o~ mag-
nesium silicate which was added as an aqueous slurry. The
neutralized product wa~ then vacuum stripped to a minimum
pressure, nitrogen stripped, and filtered. This product had
the following properties:
Total amine, meq/g 2.50
Tertiary amine, meqJg 2.46
Hydroxyl no., mg KOH/g 274
Water, wt% 0.06
p~ in 10:6 isopropanol-water 11.4
Color, Pt-Co 30
Sodium, ppm 0.2
Potas~ium, ppm 0.6
Viscosity, ~F, cs
~7 2026
~ - 100 633
Into a ten-gallon kettle were charged 5 lbs o~ the 274
hydroxyl no. PDA polyol and 151.2 g 45~ potassium hydroxide.
The reactor was then purged with prepurified nitrogen. The
initiator was dried by vacuum and nitrogen stripping to a
water content of less than 0.1%. Propylene oxide (44.3 lb)
was reacted at 105-110 C at 50 psig over a 6-7 hour period.
The reaction mixture was then digested to a minimum pressure.
The product was subsequently neutralized at 95C by stirring
two hours with 408 g of magnesium silicate which was added as
an aqueous slurry. Di-t-butyl p-cresol (22.4 g) was then
added to stabilize the product. The neutralized product was
vacuum stripped to a minimum pressure, nitrogen stripped and
10 filtered. The ~inished product, a 6200 molecular weight
polyol, had the following properties:
Run 1 Run 2
Total amine, meq/g O.26 0.26
Hydroxyl no., mg KOH/g 36.4 36.4
Water, wt% 0.017 0.01
pH in 10:6 isopropanol-water 9.5 9.6
Color, Pt-Co 25 25
Sodium, ppm 0.4 0.2
Potassium, ppm 1.6 0.3
Viscosity, F, cs
77 1114 1157
100 562 575
EXAMPLE 2
~PREPARATION OF THE 5800 MOLECULAR WEIGHT
PROPYLENE OXIDE ADDUCT OF J~"F,F,AMINE_ D-230
Eight-pounds of JEFFAMINE~ D-230 wa~ charged into a ~ive-
gallon kettle which was purged with prepurified nitrogen.
Propylene oxide (8.2 lb) was then reacted at 145-150 C at 50
psig over a 5.5-hour period. After vacuum and nitrogen strip-
ping, the product was cooled to 100C and drained from the
kettle. This product (i.e., JEFFAMINE~ D-230 alkoxylated with
s 4 moles of propylene oxide) had the following properties:
Total amine, meq/g 4.29
Tertiary amine, meq/g 4.19
Hydroxyl no., mg XOH/g 441
Water, wt % 0.008
pH in 10:6 isopropanol-water 11.4
Color, Pt-Co 25
Sodium, ppm 0.2
Potassium, ppm 0.6
Vi cosity, F, cs
77 2026
100 633
Into a ten-gallon kettle were charged 10 lb o~ the JEFFA-
MINE~ D-230-4PO adduct and 151.2 g 45% aqueous potassium
hydroxide. The reactor wa8 then purged with prepuri~ied
nitrogen. The initiator was dried to a water content o~ less
than 0.1~ using both vacuum and nitrogen stripping. Propylene
oxide (16.1 lb) was then reacted at 120-125C at 50 psig over
a four-hour period. After digestion to an equilibrium pres-
surer-the product was neutralized at 95C by stirring two
hours with 600 g of magnesium silicate which was added as an
aqueous slurry. The neutralized product was then vacuum
stripped to a minimum pressure, nitrogen stripped, and fil-
tered. The finished product had the ~ollowing properties:
Total amine, meq/g 1.62
~ertiary amine, meq/q 1.60
Hydroxyl no., mg KOH/g 160
water, wt% 0.02
pH in 10:6 isopropanol-water 10.9
Color, Pt-Co 25
Sodium, ppm 0.2
Potassium, ppm 1.3
Viscosity, F, C8
77 994
100 369
Into a ten-gallon kettle were charged 10 lb of the 160
hydroxyl No. JEFFAMINEO D-230 polyol prepared as described
above and 304 g 45% aqueous potassium hydroxide. The reactor
was then purged with prepurified nitrogen. The initiator was
then heated to 100-C and dried to a water content of less than
0.1% using both vacuum and nitrogen stripping. Propylene
oxide (48 lb) was then added at 105-110C at 50 psig over a
4.75-hour period. After digestion to an equilibrium pressure,
the product was neutralized at 99C by stirring two hours with
821 g of magnesium ~ilicate which was added as an aqueous
slurry. Di-t-butyl p-cresol (26.3 g) was then added to stabi-
lize the product. The neutralized product was then vacuum
strippod to a minimum pressure, nitrogen stripped, and fil-
tered. The finished product, i.e., the 5800 polyol, had the
following properties:
Total amine, meq/g 0.28
Tertiary amine, meq/g 0.28
Hydroxyl no., mg KOH/g 38.6
Water, wt% 0.01
pH in 10:6 isopropanol-water 9.8
Color, Pt-Co 10
Sodium, ppm 0.2
Potassium, ppm 0.2
Vlscosity, F, cs
77 1049
100 519
EXAMPLE 3
PREPARATION OF THE 5100 MOL~CULAR WEIGHT
PROPYLENE OXIDE ADDUCT OF JEFFA~INE_ D-400
Twelve pounds of JEFFAMINE D-400 was charged into a
five-gallon kettle which was then ~lushed with prepurified
nitrogen. Propylene oxide (8.7 lb) was then reacted at 145-
150C over a 5.2-hour period. The reaction mixture was then
digested two hours to an equilibrium pressure. After vacuum
and nitrogen stripping, the product was cooled to 100C and
drained from the kettle. The ~inished product (i.e., JEFFA-
MINE~ D-400 alkoxylated with 4 moles of propylene oxide) had
the ~ollowing properties: -
Total amine, meq/g 2.99
-- - Tertiary amine, meq/g 2.99
Hydroxyl no., mg KOH/g 334
pH in 10:6 isopropanol-water 10.6
Color, Pt-Co 40
14
Viscosity, F, cs
77 2458
100 664
Ten pounds o~ the JEFFAMINE~ D-400 4Po product prepared
as described above and 304 g o~ 45% aqueous potassium hydrox-
ide were charqed into a ten-gallon kettle. The reactor was
then purged with prepuri~ied nitrogen. The initiator was then
heated to 100~C and dried to a water content o~ less than 0.1%
employing both vacuum and nitrogen stripping. Propylene oxide
(70 lb) wa~ then reacted at 105-110C at 50 psig. Approxi-
mately nine hours was required ~or addition o~ the PO. After
a two-hour digestion to an equilibrium pressure, the alkaline
product was neutralized at 95-C by stirring two hours with 821
g of magnesium silicate which was added as an aqueous slurry.
Di-t-butyl-p-cresol ~26 g) was then added to stabilize the
polyol. The neutralized product was subsequently vacuum
stripped to a minimum pre~ure, nitrog-n stripped, and fil-
tered. The finished product, i.e., the 5100 molecular weight
polyol, had the ~ollowing properties:
Total amine, meq/g 0.39
Tertiar~ amine, meg/g 0.36
Hydroxyl no., mg KOH/g 44.2
Water, wt% 0.02
pH in 10:6 isopropanol-water 9.6
Color, Pt-Co 20
Sodlum, ppm 0.2
Potassium, ppm 0.2
Viscosity, F, cs
17 971
l00 463
EXAMPLE 4
CONTINUOUS REDUCTION AMINATION OF THE 6200 MOLECULAR
WEIGHT PROPYLENE OXIDE ADDUCT OF 1.2-PROPANE DIAMINE (PDA)
A 1200-cc. tubular reactor was charged with 6x8 mesh
Raney nickel. It was maintained at 2000 psig while ammonia,
hydrogen and the polyol of Example l (i.e., the 6200 molecu-
lar weight propylene oxide adduct o~ 1,2-propane diamine) were
simultaneously introduced at six sets of operating conditions.
The conditions and rQsults are shown in Table I.
EXAMPLE S
CONTINUOUS REDUCTION AMINATION OF THE 5800 MOLECULAR
~EIGHT PROPYLENE OXIDE ADDUCT OF JEFFAMINE_ D-230
The procedure of Example 4 wa8 repeated except that the
polyol of Example 2 (i.e" the 5800 molecular weight adduct
of JEFFAMINE D-230) was ~ed to th~ r~actor at four sets of
conditions, and the catalyst was th~ Ni/Cu/Cr catalyst of U.S.
Patent No. 3,654,370 to Yeakey. The conditlons and results
are shown in Tabl~ II.
EXAMPLE 6
CONTINUOUS REDUCTION AMINAT~ON OF THE 5100 MOLEC~k
WEIGHT PRO~YLENE OXIpE ADDUCT OF JEF~AMINE~ D-400
The procedure of Example 5 was essentially duplicated
except that ~he polyol introduced into the reactor was the
5100 molecular weight propylene oxide adduct of JEFFAMINE~
D-400 o~ Example 3, the catalyst wa introduced into the reac-
tor at four sets o~ conditions, and the catalyst was 825 cc
of an extruded Ni/Cu/Cr/Mo ~ormulation. Conditions and re-
sults are shown in Table III.
Examples 4, 5 and 6 show that high conversions of the
hydroxyl groups to the primary amines were obtained and that
the tertiary amine functionality present in the starting
materials was nearly completely preserved.
EXAMPLE 7
COMPARA~ly~
A one-liter stirred autoclave was charged with 15.08 g
o~ anhydrous molybdenum-promoted Raney nickel (RANEY 3100)
catalyst, and with 139.03 g o~ the polypropoxylated triethano-
lamine having the ~ollowing analy8es:
Total acetylatables, meq/g 0.549
--- Total amines, meqJg 0.16
Tertiary amines, meq/g 0.15
The autoclave was ~lushed with hydrogen, and 16.2 g
ammonia was charged. Hydrogen was introduced until the pres-
sure reached 352 psig. The autoclave was then heated over a
40-minute period to 240.7C and 839 psig. The autoclave was
held at 223.3-239C for 20 minutes thereafter, and cooled to
room temperatures. After filtration and removal of ammonia
and water by stripping the filtrate on a rotary evaporator at
99C/20 mm Hg, the product had the following analyses:
Total acetylatables, meq/g 0.738
Total amines, meq/g 0.62
Primary amine, meq/g 0.47
Tertiary amine, meq/g 0.04
This example demonstrates that with a polypropoxylated
non-hindered amine, the tertiary amine funct1onality is
severely degraded, with only 27% o~ the tertiary amine func-
tionality being retained.
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PREPARATION_OF RIM ELASTOMERS
The polyoxyalkylenepolyamines of this invention are use-
ful for producing RIM elastomers. Surprisingly, such RIM
elastomers can be molded at lower temperatures than those made
with prior art materials without exhibiting brittleness.
Lower mold temperatures are preferred because of lower energy
requirements and operational safety.
RIM elastomers are typically made by reacting an amine,
a chain extender and a polyisocyanate together in a mold.
Optional additives include catalysts, filler materials, mold
release agents and the like.
The RIM elastomers of this invention are prepared using
the polyoxyalkylenepolyamines such as the tetramine and hexa-
mine products previously described or are prepared by using
in combination a polyoxyalkylenepolyamine oP this invention
and a diamine or triamine terminated polyether (i.e., a poly-
oxyalkyleneamine having two or three terminal amine groups).
Polyethers and polyoxyalkylenepolyamines useful in preparing
the RIM elastomers have a molecular weight of 500 or more and,
preferably, at least 2000. Especially preferred are the
polyethers and polyoxyalkyleneamines of this invention, each
having a molecular weight of about 2000 to about 7000. ,
Useful polyoxyalkyleneamlne~ are exemplifled by tho~e of
the JEFFAMINE D- and ED-series which are diamine terminated
polyethers and those of the JEFFAMINED T-series which are tri-
amine terminated polyethers as previously described.
The chain extenders useful in the process of this inven-
tion are preferably difunctional. Mixtures of difunctional
and trifunctional chain extenders are also useful in this
invention. The chain extenders useful in this invention
include diols, amino alcohols, diam~nes or mixtures thereof.
Low molecular weight linear diols such as 1,4-butanediol and
ethylene glycol have been found suitable for use in this
invention. ~thylene glycol is especially preferred. These
chain extenders produce a polymer having a high glass transi-
tion temperature and/or high melting points when reacted with
a suitable diisocyanate. It has been discovered that the
polyurethane polymers of this invention which have a high
glass transition temperature and a high melting point also
show the improved propertie~ in the process of this invention.
Other chain extenders including cyclic diols such as 1,4-
cyclohexane diol and ring containing diols such as bis-
hydroxyethylhydroquinone, amide or ester containing diols or
amino alcohols, aromatic diamines and aliphatic amines are
also suitable as chain-extenders in the practice of this
invention.
The polyisocyanate used to react with the polyoxyalkylene
polyamine initiators may be aromatic or aliphatic polyisocya-
nate.
Typical aromatic polyisocyanates include p-phenylene
diisocyanate, polymethylene polyphenylisocyanate, 2,6-toluene
diisocyanate, dianisidine diisocyanate, bitolylene diisocya-
nate, napthalane-1,4-diisocyanate, bis(4-isocyanatophenyl)-
methane, bis(3-methyl-3-isocyanatophenyl)methane, bis(3-
methyl-4-isocyanatophenyl)methane, and 4,4'-diphenylpropane
diisocyanate.
Other aromatic polyisocyanates used in the practice of
the invention are methylene-bridged polyphenyl polyisocyanate
mixtures which have a functionality of from about 2 to about
4. These isocyanate compounds are produced by the phosgena-
tion of corresponding methylene bridged polyphenyl polyamines,
which are conventionally produced by the reaction of formalde-
hyde and primary aromatic amines, such as aniline in thepresence of hydrochloric acid and/or other acidic catalysts.
Rnown processes for preparing polyamines and corresponding
methylene-bridged polyphenyl polyisocyanates therefrom are
described in U.S. Patent Nos. 2,683,730; 2,950,263; 3,012,008;
3,344,162 and 3,362,979.
Usually methylene-bridged polyphenyl polyisocyanate mix-
tures contain about 20 to about 100 wt% methylene diphenyl-
diisocyanate isomers, with the remainder being polymethylene
polyphenyl diisocyanates having higher functionalities and
higher molecular weights. Typical of these are polyphenyl
polyisocyanatQ mixtures containing about 20 to 100 wt% methyl-
ene diphenyldiisocyanate isomers, of which 20 to about 95 wt~
thereof is the 4,4'-isomer with the remainder being poly-
methylene polyphenyl polyisocyanates of higher molecular
weight and functionality that have an average functionality
of from about 2.1 to about 3.5. These isocyanate mixtures
are commercially available and can be prepared by the process
described in U.S. Patent No. 3,362,979 to Floyd E. Bentley.
The most preferred aromatic polyisocyanate is methylene
bis(4~ phenylisocyanate) or MDI. Pure MDI, quasi-prepolymers
of MDI, modified pure MDI, are all useful in the preparation
of RIM elastomers. Since pure MDI is a solid and, thus, often
inconvenient to use, liquid products based on MDI are often
used and are included in the scope of the terms MDI or methyl-
24
ene ~ls(4-phenylisocyanate) us~ed herein. u.S. Patent No.
3,394,164 is an example o~ a liquid MDI product. More gener-
ally, uretonimine modified pure MDI is included also. This
product is made by heating pure distilled MDI in the presence
of a catalyst to give a mixture of pure MDI and modified MDI .
Preferably, the amount of ~socyanates used is the stoichiomet-
ric amount based on all the ingredients in the fo~mulation or
greater than the stoichiometric amount. Examples of commer-
cial materlals of this typs are Up~ohn's Isonate~ 125M (pure
MDI) and Isonate~ 143L (liquid MDI).
Although not es~ential for the practice of this inven-
tion, add$tives which enhance the color or properties of the
polyurethane elastomer may be used. For example, chopped or
milled glass fiber~, chopped or milled carbon fibers and/or
other mineral fibers are useful.
The RIM polyurethane elastomers of this invention are
made in the conventional manner in a mold at a temperature of
about 120-225F and are then post cured at a temperature of
about 225-400F and pre~erably about 225-350F.
Another type of additive, whlch mny be required as post
curing temperatures approach 400F or more, is an antioxidant.
The materials which are well-known to those skilled in the art
include hindered phenols.
The preparation of the valuable RIM elastomers is de-
scribed in the following example~ which are not to be con-
strued as limiting in any way.
.~
PREP~RA?ION OF PO~REA RIM U$I~G THE
PRODUCT OF EXA~P~ 5
JEFF~MINE0 D-2000, a polyoxyalkylenediamine of about 2000
molecular weight (28.5 pbw), diethyltoluenediamine (DETDA)
(39.0 pbw), ETHACURE~ 300, di(methylthio)toluenediamine from
Ethyl Corp. (8.0 pbw), zinc stearate (1.75 pbw), a silicone
surfactant L-5430 made by Union Carbide Chemical Corp. (0.5
pbw), and four functional polyamine 6292-15-2 of Example 5
(28.5 pbw) was charged into the B-component working tank o~
an Accuratio two component RIM machine. Quasi-prepolymer A,
prepared by reacting THANOL SF-5505, a 5000-molecular weight
high-reactive triol made by the Texaco Chemical Co. (40 pbw),
lS and ISONATE~ 143L (60 pbw) made by The Up~ohn Co., was charged
into the A-component tank. The temperatures o~ the two
streams were ad~usted to 120F and 120F, respectively. The
components were in~ected into a flat plaque mold measuring 18-
inch x 18-inch x 0.125-inch which had been preheated to 130F.
The part, removed from the mold in 30 seconds, was a brittle
elastomer. The mold temperature was then increased to 152 F
and the components were in~ected into the mold. After 30
seconds, the part removed from the mold exhibited no brit~le-
ness. This elastomer was post cured at 250F for 30 minutes.
Physical properties of the elastomer are shown in Table IV.
Similar flexural modulus, tensile, tear and shore D data is
seen for the three elastomers. Improvement in properties is
seen in higher impact values. A processing imprOvQment is
seen by the drop in the required mold temperature to process
the material. A good RIM part must be molded above the point
where the part is brittle, or it could break upon demold.
~;~
PREPARATION OF POLYUREA RIM USING
THE PRODUCT oF EXAMP~E 4
JEFFAMINE~ D-2000 (28.5 pbw), diethyltoluenediamine
(DETDA) (39.0 pbw), ETHACURE~ 300, from Ethyl Corp. (8.0 pbw),
zinc stearate (1.75 pbw), a silicone surfactant L-5430 (0.5
pbw), and a ~our ~unctional polyamine 6222-98 of Example 4
(28.5 pbw) were charged into the B-component working tank of
an Accuratio RIM two-component machine. Quasi-prepolymer A,
prepared as described in Example 8 above, was charged into the
A-~omponent tank. The temperatures of the two streams were
ad~usted to 120F and 120F, respectively. The components
were in~ected into the ~lat plaque mold which had been pre-
heated to 153F. The resulting elastomer was brittle. The
mold temperature was increased to 162F, 173F, and 183F with
the same result. Finally, at 195F, the plaque formed was not
brittle upon demold. The resulting elastomer was post cured
at 250F for 30 minutes. Physical properties of the elastomer
are shown in Table IV.
EXAMPLE 10 (COMPARATIVE)
PREPARATION OF POLYUREA RI~I USING JEFFAMINE~ D-2000
AND JEFFAMINE- T-5000 AS THE AMI~E COMPONENT
JEFFAMINEO D-2000 (28.5 pbw), diethyltoluenediamine
(DETDA) (39.0 pbw), ETHACURE~ 300, from Ethyl Corp. (8.0 pbw),
and JEFFAMINE~ T-5000, a polyoxyalkylenetriamine of about 5000
molecular weight (28.5 pbw), were charged into the B-component
working tank Or an Accuratio RIM machine. Quasi-prepolymer
A, prepared as described in Example 8 above, was charged into
the A-component tank. The temperatures of the two streams
were ad~usted to 120F and 120F, respectively. The compo-
nents were in~ected into the flat plaque mold which had been
preheatad to 150F, and after 30 seconds, the part was removed
from the mold. The resulting elastomer was brittle upon
demold. The temperature on the mold was increased to 200~F
in 10 incr~ments while in~ecting into the mold. The plaques
were brittle at these temperatures. At a mold temperature of
210F, the plaque was no longer brittle. The resulting elas-
tomer was post cured at 250F for thirty minutes. Physical
properties of the elastomer are shown in Table IV. As can be
seen from the table, improved i20d impact values can be
achieved relative to the comparative Example 10. Also, lower
mold temperatures can also be achieved. It is common for
thermal properties to decrease somewhat when lower mold tem-
peratures are used.
TABL~EY
PHYSICAL PROPERTI~S_OF THE POLYUREA
PRODUCTS OF EX~ME'LES 8, 9 AND 10
Example No. 8 9 10
Shore D, instant/10 seconds 67/63 67/62 66/62
Tensile, pli 4661 4958 4894
Tear, psi 653 675 693
Ultimate elongation, % 197 220 217
Flexural modulus, psi
-20F 195000186000 182000
77F 94000 91000 93000
158F 65900 70500 67500
311F 40000 44500 46000
Heat sag
311F, 150mm 19 14 9.5
Izod Impact, ft-lbs/in of notch4.3 3.6 2.8
Lowest mold temperature before
brittleness occurred, ~F 152 195 210
Table o~ Test MethQds
Tenslle, p~i ASTM D-638
Tear, pli ASTM D-624
Ultimate elongation, % ASTM D-638
Flexural modulus, psi ASTM D-790
Izod impact, ft-lb/in. notchASTM D-256
Heat sag, mm Heat sag is determined in accordance
with Test CTZZZ0066AA of the Chev~ro-
let Division o~ General Motors Cor~po-
ration, Flint, MI, and i8 the sample
sag in millimeters when exposed to
the speci~ied temperature ~or 60
minutes.
29
PREP~RATION OF EPOXY RESINS
This invention also relatees to an epoxy resin composition
comprising a vicinal polyepoxide having an epoxide equivalency
of greater than or equal to about 1.8, and a curing amount of
a curing agent comprising a polyoxyalkylenepolyamine, for
example, including, but not limited to the JEFFAMINE~ D-ser-
ies, T-series and EDR-series amines, and an amine selected
from the group consisting of:
(1) A Type-A compound of the formula:
o R~ CH3 Cl H3 1 ' l H3 ~R
~N-CHCH2ttOCH2 CHt~tOCH2 CHt~OCH2 CHt~ N
R R
where a + b + c = 2-100 and wherein R i8:
R' C~ CH3
- ( CH2 CHOt~CH2 CHOt;~CH2 CH-NH2
R ' is selected from the group consisting of hydrogen
and the methyl or ethyl radical,
x ranges from 0 to about 10,
y rangQs from 2 to about 100,
n is 0 or 1, and with the provlso that when n is 0,
then Rl is the methyl or ethyl radical; and
(2) A Type-B compound of the formula:
CH3 R
I
CH ~ OCH 2CH ~N~
R
CH3 /R
R ~ - ( ` ~ CH 2~0CH 2CH 3 e N~
CH3 R
H I /
~ OCH 2CH t~ N\
wherein R" is selected from the group consisting of hydro-
gen and the methyl or ethyl radical,
z is 0 or 1,
R has the same meaning as previously described
in (1) above and the sum o~ d + e + f ranges
from 3 to 100.
Polyoxyalkylenepolyamines useful in preparing the epoxy
resin compositions of this invention have molecular weights
of about 148 or more and include, for example, diamines of'the
JEFFAMINE~ D-series, the JEFFAMINE~ EDR-series, or triamines
~rom the T-series such as T-403. Suitable polyoxyalkylenedia-
mines of the JEFFAMINE EDR-series include, for example:
JEFFAMINE EDR-148 having the formula:
H,N - CH,CH, - 0 - CH,CH, - 0 - CH,CH, - NH,
The resulting cured epoxy resin compositions are clear
materials especially suitable as castings or adhesives for use
in electrical or electronic applications.
Ta~les V-VI show 24-53 wt.~ of the Type A or B compound
with the remainder being polyoxyalkylenediamine. Usually the
curing agent will comprise from about 15 to about 60 weight
percent of the Type A or Type ~ compound with the balance
being the polyoxyalkylenediamine.
Generally, the amine-cured, vicinal polyepoxide-contain-
lo ing compositions are organic materials having an averag~ ofat least 1.8 reactive 1,2-epoxy groups per molecule. These
polyepoxide materials can be monomeric or polymeric, saturated
or unsaturated, aliphatic, cycloaliphatic, aromatic or hetero-
cyclic, and may be substituted if desired with other substitu-
ents besides the epoxy groups; e.g., hydroxyl groups, etherradicals, aromatic halogen atoms and the like.
Preferred polyepoxides are those of glycidyl ethers pre-
pared by epoxidizing the corresponding allyl ether~ or react-
ing, by known procedures, a molar excess o~ epichlorohydrin
and an aromatic polyhydroxy compound; i.e., isopropylidene
bisphenol, novolak, resorcinol, etc. ~he epoxy derivatives
o~ methylene or isopropylidene blsphenols are especially
preferred.
A widely used class of polyepoxides which are useful
according to the ~nstant invention includes the resinous epoxy
polyethers obtained by reacting an epihalohydrin, such as
epichlorohydrin, and the like, with either a polyhydric phenol
or a polyhydric alcohol. An illustration, but by no means
exhaustive, liating of suitable dihydric phenols includes
4,4'-isopropylidene bisphenol, 2,4'-dihydroxydiphenylethyl-
methane, 3,3'-dihydroxydiphenylcliethylmethane, 3,4'-dihydroxy-
diphenylmethylpropylmethane, 2,3'-dihydroxydiphenylethylpro-
pylmethane, 4,4'-dihydroxydiphenylpropylphenylmethane, 4,4'-
dihydroxydlphenylbutylphenylmethane, ~,2'-dihydroxydiphenyldi-
tolylmethane, 4,4'-dihydroxydiphenylitolylmethylmethane, and
the like. Other polyhydric phenols which may also be co-
reacted with an epihalohydrln to provid~ these epoxy poly-
ethers are such compounds as resorcinol, hydroquinone, substi-
tuted hydroquinones; e.g., methylhydroquinone, and the like.
Among the polyhydric alcohols which can be co-reacted
with an epihalohydrin to provide these resinous epoxy poly-
ethers are such compounds as ethylene glycol, propylene gly-
cols, butylene glycol~, pentane diols, bis(4-hydroxycyclo-
hexyl)dimethylmethane, 1,4-dimethylolbenzene, glycerol, 1,2,6-
hexanetriol, trimethylolpropane, mannitol, sorbitol, eryth-
ritol, pentaerythritol, their dimers, trimers and higher poly-
mers; e.g., polyethylene glycols, polypropylene glycols, tri-
glycerol, dipentaerythritol and the like, polyallyl alcohol,
polyhydric thioether~, such as 2,2'-, 3,3'-tetrahydroxydipro-
pylsulfide and the like, mercapto alcohols such as monothio-
glycerol, dithioglycerol, and the like, polyhydric alcohol
partial esters, such as monostearin, pentaerythritol monoace-
tate, and the like, and halogenated polyhydric alcohols such
as the monochlorohydrins o~ glycerol, sorbitol, pentaeryth-
ritol and the like.
Another class o~ polymeric polyepoxides which can be
amine-cured and are in accordance with the instant invention
includes the epoxy novolak resins obtained by reacting, pref-
erably in the presence of a basic catalyst; e.~., sodium or
potassiu~ hydroxide, an epihalohydrin, such as epichlorohy-
drin, with the resinous condensatQ of an aldehyde; e.g., for-
maldehyde, and either a monohydric phenol; e.g., phenol it-
self, or a polyhydric phenol. Further details concerning the
nature and preparation of these epoxy novolak resins can be
obtained in Lee, H. and Neville, K., ~andbook of Epoxy Resins,
McGraw-Hill ~ook Co., New York, 1976.
Other polyepoxides known to those skilled in the art may
be useful in this invention.
Optionally, the epoxy resin formulations of the instant
invention can include an "accelerator" to speed the amine cure
of the epoxy resin, especially at ambient temperatures. In
several app~ications, such acceleration is beneficial, espe-
cially when an epoxy resin i8 used as an adhe~ive in flammable
environment, thus making elevnted temperature cure inconven-
ient or even hazardous. Lee, H. and Neville, K., ~andbook of
Epoxy Reslns, pp. 7-14, describes the use of certain amine-
containing compounds as epoxy curing agent-accelerators.
Many accelerators are known in the art which can be
utilized in accordance with the instant invention. Examples
include salts of phenols, salicyclic acid~, amine salts of
fatty acids, such as tho~e disclosed in U.S. Patent No.
2,681,901, and tertiary amine~ such as those disclosed in U.S.
Patent No. 2,839,480. Preferred accelerators in accordance
with the in~tant invention are disclosed in U.S. Patent Nos.
3,875,072 and 4,195,153.
It will further be realized that various conveniently
employed additives can be admixed with the polyepoxide-con-
talnlnq composition of the instant invention prior to final
cure. For example, in certain instances it may be desired to
add minor amounts of hardeners along with various other accel-
erators and curing agent systems well-known in the art.
Additionally, conventional pigments, dyes, fillers, flame-
retarding agents and the like which are compatible; natural
or synthetic resins can be added.
The following examples illustrate the nature of the in-
stant invention but are not intended to be limitative there-
of.
EXAMPLE 11
This example illustrates the use of the polyoxyalkylene-
polyamines of this invention in preparing clear epoxy castings
and adhesives. Formulations, dQtails of preparation and
propertie~ of the cured epoxy procucts are set out in Table
V which follow~. Runs A and B shown in Table V are examples
of the clear, cured, epoxy resin compositions of this inven-
tlon which exhibit highly satis~actory physical properties,
while Runs C and D are comparative runs showing that opaque,
cured, epoxy resin compositions result when the curing agent
comprises prior art materials, such as JEFFAMINE~ T-5000.
TABLE ~
PROPERTIES OF EPOXY RESIN PRODUCTS ÇU~ WITH ~LENDS OF
THE 6292-73-2 PRODU~T OF EXAMPI~ 6 A~p JEFFAMINE- D-230
(Elevated Temperature Cure)
Formulation, Pbw A 9 C D
Liquid epoxy resin
(epoxy equiv. wt 188)100 100 100 100
JEFFAMINE~ D-230 31 30 31.2 30.5
6292-73-2 Prod. of Ex. 610 20
JEFFAMINE~ T-5000 - - 10 20
Casting clear clear opaque opaque
Prope~ties Or ~ured 1/8-inch Castinas
Cured 2 hours 0 80C, 3 hours @ 125C
Shore D hardness, O-lo sec. 79-74 75-70 70-66 68-64
HDT, C, 264 psi/66 p8i load66/73 54/65 70/77 63/72
Izod impact strength, ft-lb/in0.16 0.25 0.22 0.36
Tensile strength, psi7800 6100 8000 6500
Tensile modulus, psi360000290000310000 250000
Elongation, % 8.1 12.1 8.7 8.1
Flexural strength, psi1300010800 14200 10300
Flexural modulus, p8i365000287000367000283000
Adhesion Prope~ies
Cured 1 hour Q 125 C
Tensile shear strength, p5i4100 3800 4600 3~00
T-peel strength, p8i 2.3 4.4 9.4 18~8
The liquid epoxy re~in is Epon9 828, a diglycidyl ether of Bisphe-
nol A.
Results reported in Table VI which follows illustrate the
use of the polyoxyalkylenepolyamines of this invention to make
mo~e compatible epoxy resin systems. Castings and adhesives
prepared as set out in Runs E and F of Table VI, which utilize
the polyoxyalkylenepolyamines of this invention, possess good
physical properties. Runs G and H are comparative runs which
show the use of prior art epoxy curing agents. Formulations,
details of preparation and properties of the products are
shown in Table VI.
TABLE VI
PROPERTIES OF ~POXY RESIN PRODUCTS CURED WITH BLENDS OF
THE 6292-73-2 PRODUCT OF EXAMPLE 6 AND JEFFAMINE- EDR-148
(Elevated Temperature Cure)
Formulation Pbw E F G H
Liquid epoxy resin
(epoxy equiv. wt 188)100 100 100 100
JEFFAMINE~ EDR-148 18.6 18.0 19.8 19.3
6292-73-2 Prod. o~ Ex. 610 20
JEFFAMINE~ T-5000 - - 10 20
Casting opaque opaque opaque opaque
Pro~erties of Cured 1/8-inch Castinas
Cured 2 hours ~ 80C, 3 hours ~ 125C
Shore D hardness, 0-10 sec. 76-71 76-68 70-65 (1)
HDT, C, 264 psi/66 psi load 75/8270/77 80/88
Izod impact strength, ft-lb/in0.30 0.27 0.20
Tensile strength, p8i7400 6200 7800
Tensile modulus, p8i350000 270000250000
Elongation, ~ 8.6 9.0 9.9
Flexural strength, p8i12600 1020011500
Flexural modulus, p8i324000 400000293000
Adhesion Pro~erties
Cured 1 hour Q 125C
Tensile shear strength, psi 4200 3800 4300
T-peel strength, p8i 3.2 5.5 - `
(1) System not compatibles no properties detQrmined.
JEFFAMINE~ EDR-148 is triethylene glycol diamine.
38
