Phenol-aldehyde condensation product with aminoalkylene derivative of a polyoxyalkylenepolyamine

Abstract

A process for the accelerated cure of an epoxy resin is disclosed. The resulting epoxy resin may be used in protective coatings, adhesives, seamless and terrazo flooring and caulking and sealing compositions. The resulting resin system is also useful, for example, in casting, potting, in escapulating, grouting and patching. The process involves mixing an epoxy resin of the polyhydric phenol, polyglycidyl ether type with a novel accelerator-hardener which is a condensation product of phenol, formaldehyde and an aminoalkylene derivative of a polyoxyalkylenepolyamine.

Description

BACKGROUND OF THE INVENTION

The present invention relates to the field of curing epoxy resins.

Polyoxypropylenepolyamines react with epoxy resins at a rate which is unsatisfactorily slow for certain applications. In order to provide a rate of cure which is satisfactory for most uses an accelerator must be used with the polyoxypropylenepolyamines in order to speed the rate of cure.

Lee, Henry and Neville, Kris, Handbook of Epoxy Resins, McGraw-Hill Book Co., N.Y., 1967, p. 7-14, describes the use of N-(2-aminoethyl)piperazine as an epoxy curing agent and at page 11-18 describes the use of salicylic acid as an accelerator for urea-formaldehyde epoxy resin coatings. Bobby Leger's U.S. Pat. No. 3,462,393 (Aug. 18, 1969) teaches the use of polyoxyalkylenepolyamines as curing agents for a polyglycidyl ether of a phenolic compound.

U.S. Pat. No. 3,639,928 claims the use of a combination of N-(3-aminopropyl)piperazine and salicylic acid as an accelerator combination with polyoxyalkylenepolyamine for curing epoxy resins.

U.S. Pat. No. 3,734,965 describes the use of a condensation product of phenols, aldehydes and polyoxypropyleneamines.

SUMMARY OF THE INVENTION

The invention is a process for the accelerated cure of an epoxy resin composition of the polyhydric phenol, polyglycidyl ether type. The process involves mixing the epoxy resin with an accelerator-hardener which is a condensation product of phenol, formaldehyde and an aminoalkylene derivative of a polyoxyalkylenepolyamine. The invention is also the condensation product above and the resulting cured epoxy resin.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The epoxy resin used herein can be any of the well known epoxy resins having an epoxy equivalency of more than one, for example, the polyglycidyl ether of polyhydric phenol. As is well known in the art, these resins may be prepared by condensing epichlorohydrin with a polyhydric alcohol or phenol, for example, ethylene glycol, diethylene glycol, glycerol, diglycerol, catechol, resorcinol, a trihydroxybenzene, a di(hydroxyphenyl) methane, a di(hydroxyphenyl) ethane, a di(hydroxyphenyl) propane, etc. The epoxy resin is derived from condensing epichlorohydrin with 2,2-bis(p-hydroxyphenyl) propane, known generally as bisphenol-A and having an epoxide equivalent weight of from 175 to 195.

The aminoalkylene derivatives of polyoxyalkylenepolyamines can be made by reacting polyoxyalkylenepolyamines with acrylonitrile followed by hydrogenation of the product. For example, polyoxypropylenepolyamines used as starting materials include compounds of the following formulae:

H.sub.2 NCH(CH.sub.3)CH.sub.2 [(OCH.sub.2 CH(CH.sub.3)].sub.x NH.sub.2 ( 1) where x=2 to 40 and ##STR1## where x+y+z=3 to 40 and ##STR2## where x+z=2 to 10 and y=1 to 50

After reaction with acrylonitrile and subsequent hydrogenation the resulting aminoalkylene derivative of polyoxyalkylenepolyamines have the following formulae:

H.sub.2 NCH.sub.2 CH.sub.2 CH.sub.2 HNCH(CH.sub.3)CH.sub.2 [OCH.sub.2 CH(CH.sub.3)].sub.x NHCH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2 ( 1A) where x=2 to 40 and ##STR3## where x+y+z=3 to 40 and ##STR4## where x+z=2 to 10 and y=1 to 50

It is preferred to use phenol but substituted phenols are also useful in the condensate. The substituted phenols include, for example, mono- or polyhydric phenols with at least one reactive nuclear position available for substitution (o or p.). Examples: o-, m-, p-cresol, resorcinol, pyrocatechol, hydroquinone, phloroglucinol, pryogallol, .alpha. and .beta.-naphthol, p-tert-butylphenol, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxydiphenylsulphone. It is preferred to use formaldehyde but useful aldehydes include both aliphatic and aromatic aldehydes, for example: acetaldehyde, butyraldehyde, benzaldehyde. Aldehydes of the general formula below are useful:

RHCO wherein R=H--, CH.sub.3 --, C.sub.2 H.sub.5 --C.sub.4 H.sub.9 or

The preparation of the condensation product is performed as follows but obvious deviations from this scheme are included in our invention: phenol, formaldehyde and a small amount of triethylamine is heated at reflux (.about.100.degree. C.) for 1-2 hours and then cooled to <50.degree. C. Amine (aminoalkylene derivative of polyoxyalkylenepolyamines) addition is begun while raising the temperature to about 165.degree. C. while water is removed. Water is removed until overhead temperature drop is noted. The product is then vacuum stripped at 150.degree. C./30mm for 2-4 hours.

The pressure is atmospheric except where vacuum stripping is noted. No pH adjustment is made during the reaction. The ratio of aminoalkylene derivative of polyoxyalkylenepolyamine/phenol/formaldehyde may range about 3/1/1 to 1/1/1. These variables are only guidelines and should not be construed as limitative of the invention claimed hereinafter.

For curing epoxy resins, the hardening agent (the condensate herein) is usually added in an amount such that there is one reactive -NH group in the hardener component for each epoxy group in the epoxy resin component. These are known as stoichiometric quantities. The stoichiometric quantity can be calculated from a knowledge of the chemical structure and analytical data on the components. In general it is advantageous to use up to 10 percent excess of the accelerated hardener over the stoichiometric amount.

The curing temperature range of the ambient temperatures are from about 0.degree. to about 45.degree. C. Post cures at temperatures up to about 200.degree. C. are optional. The cured epoxy resins of the invention are useful in castings, coatings, adhesives, laminates, filament-reinforced composites, seamless flooring, terrazzo flooring, crushed-stone aggregates and in grouting, caulking and sealing compositions.

EXAMPLE I

Preparation of a condensate of the aminopropylene derivative of a 230 molecular weight polyoxypropylenepolyamine with phenol and formaldehyde.

______________________________________Reactants:______________________________________JEFFAMINE.RTM.D-230 Bis(propylamine)* 1338 g.(JEFFAMINE.RTM.D-230 BPA)Phenol 355 g.Formaldehyde 306 g. (37% soln.)Triethylamine(TEA) 10 g.______________________________________ *JEFFAMINE D230 is a polyoxypropylenepolyamine of formula I (x is about 2.6) and JEFFAMINE D230 Bis(propylamine) is the aminopropylene derivative of JEFFAMINE D230.

The phenol, formaldehyde and TEA were added to a reactor and heated to reflux temperature (about 100.degree. C.) for 2 hours and then cooled to 95.degree. C. The JEFFAMINE D-230 BPA was added to the mixture in the reactor while raising the temperature to about 135.degree. C. The product was then vacuum stripped at 130.degree. C./30mm for 2 hours.

EXAMPLE II

Preparation of a condensate of the aminopropylene derivative of a 400 molecular weight polyoxypropylenepolyamine with phenol and formaldehyde.

______________________________________Reactants:______________________________________JEFFAMINE.RTM.D-400 Bis(propylamine)* 1368 g.Phenol 259 g.Formaldehyde 223 g. (37% soln.)Triethylamine (TEA) 9.25 g.______________________________________ *JEFFAMINE D400 is a polyoxypropylenepolyamine of formula I (x is about 5.6) and JEFFAMINE D400 Bis(propylamine) BPA is the aminopropylene derivative of JEFFAMINE D400.

The procedure in Example I was followed except the maximum temperature of the reactor was 165.degree. C. prior to vacuum stripping.

EXAMPLE III

ACCELERATION OF CURE THROUGH USE OF PHENOL-FORMALDEHYDE CONDENSATE OF AN AMINOALKYLENE DERIVATIVE OF A POLYOXYALKYLENEPOLYAMINE

______________________________________Formulation: A B C D______________________________________Epoxy resin (EEW 190) 100 100 100 100JEFFAMINE D-400 Bis(propylamine) 46 -- -- --JEFFAMINE D-400 BPA** . Phenol .Formaldehyde Condensate -- 52 -- --JEFFAMINE D-230 Bis(propylamine) -- -- 30 --JEFFAMINE D-230 BPA . Phenol .Formaldehyde Condensate -- -- -- 38Gel time, mins. (200 g. mass) 160.3 92.4 73.5 30.8Peak Exotherm, .degree.C. 160.0 126.5 224.0 213.0Time to peak, mins. 178.0 114.0 85.0 43.0______________________________________

EXAMPLE IV

DEVELOPMENT OF ADHESION: CURING WITH PHENOL.FORMALDEHYDE CONDENSATE VS. JEFFAMINE D-230 BPA

______________________________________Formulation A B______________________________________Epoxy resin (EEW 185) 100 100JEFFAMINE D-230 Bis(propylamine) 30 --JEFFAMINE D-230 BPA . Phenol .Formaldehyde Condensate -- 38Tensile shear strength, psiafter curing for: 4 hours <5 0 8 hours 900 110016 hours 2200 290024 hours 1200 3000______________________________________

EXAMPLE V

COMPARISON OF CONDENSATION PRODUCT OF THIS INVENTION WITH SIMILAR CONDENSATE USING POLYOXYPROPYLENEAMINES

Comparison of Properties: Curing with JEFFAMINE D-400; D-400.Phenol.formaldehyde Condensate with BPA D-400.Phenol. formaldehyde Condensate

______________________________________Formulation: A B C______________________________________Epoxy resin (EEW 185) 100 100 100JEFFAMINE D-400 50 -- --D-400 . Phenol . CH.sub.2 O Cond. -- 75 --BPAD-400 . Phenol . CH.sub.2 O Cond. -- -- 55Brook. visc., cps., R.T. 500 3800 4700Gel time, mins (200 g. mass) .about.300 142 28.3Peak exotherm, .degree.C. -- 71.5 164.0Time to peak temp., mins. -- 180 38.0Drying time, 6-mil filmSet-to-touch, hrs. 13.3.sup.2 9.9 4.0Thru-dry, hrs. 15.2 13.2 5.0Rev. impact, in-lbs to failcure: 24 hr., R.T. >160 148 >160 7 day, R.T. >160 12 20 14 day, R.T. >160 100 100Properties of cured 1/8" castings:.sup.1Izod impact strength, ft-lbs/in. 0.52 0.97 0.94Tensile strength, psi 8200 9100 9300Tensile modulus, psi 399000 456000 438000Elongation at break, % 3.7 4.6 6.0Flexural strength, psi 12200 13200 14200Flexural modulus, psi 400000 447000 457000HDT, .degree.C., 264 psi/66 psi 41.5/42 46/50 56/59Shore D hardness, 0-10 sec. 80-77 84-82 86- 85% wt. gain, 1 hr. acetone boil -- 13.67 5.36% wt. gain, 24 hr. H.sub.2 O boil -- 2.34 2.94.sup.1 Cured 2 hrs. 80.degree., 3 hrs. 125.degree. C..sup.2 D-400 Concn. = 55 phr.______________________________________Comparison of Properties: Curing with JEFFAMINE D-400,D-300 . Phenol . CH.sub.2 O Condensate and BAPD-400 . Phenol . CH.sub.2Condensate (Acc. Curing, R.T.)Formulation: A B C______________________________________Epoxy resin (EEW 185) 100 100 100JEFFAMINE D-400 45 -- --D-400 . Phenol . CH.sub.2 O Cond. -- 75 --BPAD 400 . Phenol . CH.sub.2 O Cond. -- -- 55Acc. 398 10 10 10Brook. visc., cps., R.T. -- 3800 5000Gel time, mins. (200 g. mass) 41.0 31.2 14.2Peak exotherm, .degree.C. 163.0 164.0 194.0Time to peak, mins. -- 42.0 19.5Drying time, 6-mil filmSet-to-touch, hrs. 8.3 6.0 2.0Thru-dry, hrs. 11.8 8.8 3.0Rev. impact, in-lbs to failCure: 24 hr., R.T. >160 >160 >160 1 hr. 110.degree. C. >160 > 160 80 7 day, R.T. >160 88 20 14 day, R.T. >160 >160 80Properties of cured 1/8" castings:.sup.1Izod impact strength, ft-lbs/in. 0.62 0.88 0.98Tensile strength, psi 7500 7000 9600Tensile modulus, psi. 388000 418000 452000Elongation at break, % 5.1 20.8 5.0Flexural strength, psi. 9900 10900 15100Flexural modulus, psi. 335000 336000 451000HDT, .degree.C., 264 psi/66 psi 40/42.5 37/39 48/49Shore D hardness, 0-10 sec. 83-80 82-80 82-80% wt. gain, 1 hr. acetone boil -- 14.40 9.06% wt. gain, 24 hr. H.sub.2 O boil -- 4.67 3.75______________________________________ .sup.1 Cured 7 days, R.T.

It is clear from the above example that the drying times and touch times are much less using the condensate of the invention than with the prior art condensate or using polyoxypropyleneamines alone.

Claims

1. The condensation product of phenol, formaldehyde and an aminoalkylene derivative of a polyoxyalkylenepolyamine made by reacting a polyoxyalkylenepolyamine with acrylonitrile followed by hydrogenation.

2. The condensation product of phenol, formaldehyde and an aminopropylene derivative of a polyoxypropylenepolyamine made by reacting a polyoxypropylenepolyamine with acrylonitrile followed by hydrogenation.

3. The condensation product of phenol, formaldehyde and an aminopropylene derivative of a polyoxypropylenepolyamine of about 400 molecular weight made by reacting a polyoxypropylenepolyamine of about 400 molecular weight with acrylonitrile followed by hydrogenation.

4. The condensation product of phenol, formaldehyde and an aminopropylene derivative of a polyoxypropylenepolyamine of about 230 molecular weight made by reacting a polyoxypropylenepolyamine of about 230 molecular weight with acrylonitrile followed by hydrogenation.

5. The condensation product of a phenolic compound, an aldehyde and an aminoalkylene derivative of a polyoxyalkylenepolyamine made by reacting a polyoxyalkylenepolyamine with acrylonitrile followed by hydrogenation.