CA2030443A1 - Polyamines by amination of polyamino initiated polyoxyalkylene glycols - Google Patents

Abstract

POLYAMINES BY ANINATION OF POLYAMINO
INITIATED POLYOXYALKYLENE GLYCOLS

ABSTRACT OF THE DISCLOSURE
A process in which a polyamine initiator is oxyalkylated to form the corresponding polyamine polyoxyalkylene glycol which is then catalytically aminated to provide a polyoxyalky-lenepolyamine is disclosed. These compounds are useful as curing agents for epoxy resins and for reaction with isocya-nates to manufacture articles, such as automotive body panels, by reaction injection molding.

Description

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:

CH ~ OCH 2CH ~ ~( R

R - C ~ CH 2~0CH 2CH-~ e 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:

,, , (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 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:

H2NlHCH~OCH2CHt5 6 NH2 ~EF~AMINE D-2000 having the ~ormula:

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 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 H H
Cl~ O ~ CH2 1 0 Ih Cl~ 1 ~2 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 ~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 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 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 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 Viscosity, F, cs 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 l00 463 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

~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.

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.

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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,~ L, 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-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 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.

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:

I
CH ~ OCH 2CH ~N~
R

R ~ - ( ` ~ CH 2~0CH 2CH 3 e N~

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.

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

(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.

Claims (23)

1. A polyamine selected from the group consisting of:
(1) a Type A compound of the formula:

wherein a + b + c = 2-100 and R is:

R' is selected from the group consisting of hydro-gen and the methyl or ethyl radical, x ranges from 0 to about 10, y ranges from 2 to about 100, and n is 0 or 1, and with the proviso that when n is 0, then R' is the methyl or ethyl radical; and (2) a Type B compound of the formula:

wherein R" is selected from the group consisting of hydrogen and the methyl or ethyl radical, z is 0 or 1, R has the same meaning as previously de-scribed in (1) above and the sum of d +
e + f ranges from 3 to about 100.

2. The polyamine of Claim 1 wherein the said polyamine is a Type A compound.

3. The polyamine of Claim 1 wherein the said polyamine is a Type A compound wherein n is 0 and R' is the methyl radical.

4. The polyamine of Claim 1 wherein the said polyamine is a Type A compound wherein n is 1 and R' is the methyl radical.

5. The polyamine of Claim 1 wherein the said polyamine is a Type A compound.

6. A process for producing a polyoxyalkylenepolyamine which comprises:
(1) alkoxylating an amine selected from the group consisting of (i) an alkylenediamine, (ii) a polyoxyalkylene-diamine, and (iii) a polyoxyalkylenetriamine to form the corresponding polyamine polyoxyalkylene glycol having at least two terminal groups of the structure:

wherein X is a hydroxyl terminated polyoxyalkylene group and x' is independently selected from the group consisting of hydrogen and the methyl or ethyl radical and with the proviso that in at least one of the terminal groups, X' is the methyl radical, and when X' is hydrogen, the oxyalkylene segment of the polyoxyalkylene groups attached to the nitrogen atom bear a pendant methyl or ethyl radical; and (2) catalytically aminating the said glycol with ammonia in the presence of hydrogen to form the polyoxyalky-lene polyamine.

7. The process of Claim 6 wherein the said amine is an alkylenediamine.

8. The process of Claim 6 wherein the said polyamine is a polyoxyalkylenediamine.

9. The process of Claim 6 wherein the said amine is a polyoxyalkylenetriamine.

10. A reaction injection molding process comprising reacting in a closed mold ingredients comprising an amine, an active hydrogen-containing chain extender and a polyisocyanate wherein the said amine is selected from the group consisting of:

(1) a Type A amine of the formula:

wherein a + b + c = 2-100 and R is:

R' is selected from the group consisting of hydro-gen and the methyl or ethyl radical, x ranges from 0 to about 10, y ranges from 2 to about 100, and n is 0 or 1, and with the proviso that when n is 0, then R' is the methyl or ethyl radical; and (2) a Type B amine of the formula:

wherein R" is selected from the group consisting of hydrogen and the methyl or ethyl radical, z is 0 or 1, R has the same meaning as previously de-scribed in (1) above and the sum of d +
e + f ranges from 3 to about 100; and (3) a Type C amine which comprises a Type A amine or a Type B amine and an amine selected from the group con-sisting of a polyoxyalkylenediamine and a polyoxyalkylenetria-mine.

11. The process of Claim 10 wherein the said amine is a Type A compound.

12. The process of Claim 10 wherein the said amine is a Type A compound wherein n is 1 and R' is the methyl radical.

13. The process of Claim 10 wherein the said amine is a Type B compound.

14. The process of Claim 10 wherein the said amine is a Type C amine comprising a Type A amine and a polyoxyalkyl-enediamine.

15. The process of Claim 10 wherein the molecular weight of the said amine is at least about 3000.

16. The process of Claim 10 wherein the molecular weight of the said amine is about 3000 to about 7000.

17. An epoxy resin composition comprising a vicinal polyepoxide having an epoxide equivalency of greater than about 1.8 and a curing amount of a curing agent comprising a polyoxyalkylenepolyamine and an amine selected from the group consisting of:
(1) a Type A compound of the formula:

wherein a + b + c = 2-100 and R is:

R' is selected from the group consisting of hydro-gen and the methyl or ethyl radical, x ranges from 0 to about 10, y ranges from 2 to about 100, and n is 0 or 1, and with the proviso that when n is 0, then R" is the methyl or ethyl radical; and (2) a Type B compound of the formula:

wherein R" is selected from the group consisting of hydrogen and the methyl or ethyl radical, z is 0 or 1, R has the same meaning as described in (1) above and the sum of d + e + f ranges from 3 to about 100.

18. The epoxy resin composition of Claim 17 wherein the said curing agent comprises a polyoxyalkylenediamine and a Type A amine.

19. The epoxy resin composition of Claim 17 wherein the said curing agent comprises a polyoxyalkylenediamine having a molecular weight of about 230 and a Type A amine wherein n is 1 and R' is the methyl radical.

20. In a method for curing a vicinal polyepoxide having an epoxide equivalency of greater than about 1.8 wherein an effective amount of a curing agent is intimately mixed with the vicinal polyepoxide under epoxy resin curing conditions, the improvement which comprises using as a curing agent a polyoxyalkylenediamine and an amine selected from the group consisting of:
(1) a Type A compound of the formula:

wherein a + b + c = 2-100 and R is;

R1 is selected from the group consisting of hydro-gen and the methyl or ethyl radical x ranges from 0 to about 10, y ranges from 2 to about 100, and n is 0 or 1, and with the proviso that when n is 0, then R' is the methyl or ethyl radical; and (2) a Type B compound of the formula:

wherein R" is selected from the group consisting of hydrogen and the methyl or ethyl radical, z is 0 or 1, R has the same meaning as described in (1) above and the sum of d + e + f ranges from 3 to about 100.

21. The polyamine of claim 1 wherein the said polyamine is a Type A compound, wherein n is 1 and R' is the ethyl radical.

22. The polyamine of claim 1 wherein the said polyamine is a Type A compound, wherein n is 1, R' is methyl and the sum of x + y ranges from about 2 to 50.

23. The polyamine of claim 1 wherein the said polyamine is a Type A compound, wherein n is 1, R' is methyl and the sum of a + b + c ranges from about 3 to about 33.