CA1116336A - Accelerated cure of epoxy resins - Google Patents
Accelerated cure of epoxy resinsInfo
- Publication number
- CA1116336A CA1116336A CA000316369A CA316369A CA1116336A CA 1116336 A CA1116336 A CA 1116336A CA 000316369 A CA000316369 A CA 000316369A CA 316369 A CA316369 A CA 316369A CA 1116336 A CA1116336 A CA 1116336A
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- Prior art keywords
- phenol
- derivative
- hydrogenation
- condensation product
- reacting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
- C08G59/623—Aminophenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/14—Block or graft polymers prepared by polycondensation of aldehydes or ketones on to macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
ACCELERATED CURE OF EPOXY RESINS
ABSTRACT OF THE DISCLOSURE
D#75,656 -F
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 re-sulting 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.
-I-
ABSTRACT OF THE DISCLOSURE
D#75,656 -F
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 re-sulting 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.
-I-
Description
33~i 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 appli-cations. In order to provide a rate of cure which is satis-factory ~or 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 Boo~ 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.
; 15 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. Patent No~ 3,639,928 claims the use of a combination of N-(3-aminopropyl)piperazine and salicylic acid as an accelerator comblnation with polyoxyalkylenepoly-amine fox curing epoxy resins.
U.S. Patent 3,734,965 describes the use of a condensation produc~ of phenols, aldehydes and polyoxy-propyleneamines.
:, SUMMARY OF THE INVENTION
The invention i~ 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 con-densation product of phenol, formaldehyde and an ~ ".
,.j:
:, . .
,~
aminoalkylene derivative of a polyoxyalkylenepolyamine. Thus, in its broad-est aspect the invention provides a process for curing epoxy resins comp-rising mixing an epoxy resin in about stoichiometric amounts with a conden-sation product of a phenolic compound, an aldehyde and an aminoalkylene derivative of a polyoxyalkylenepolyaml.ne made by reacting a polyoxyalkylene-polyamine with acrylonitrile followed by hydrogenation. 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 poly-glycidyl 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-hydro-xyphenyl) 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, pdlyoxypropylenepolyamines used as starting materials include compounds of the following formulae:
2NcH(cH3)cH2~oc~2cH(cH3)~xNH2 where x = 2 to 40 and (II) CH2(0CH2CIH)XNH2 ¦ CH3 R-C~H2 (0CH2CIH)yNH2 ~- ¦ CH3 CH2(0CH2lH)ZNH2 ~6336 where x + y + z = 3 to 40 and (III) H2NCHCH2(0CHCH2)x(OCH2CH2)y( 2 z 2 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:
NCH2CH2CH2HNCH(CH3)CH2[OCH2CH(CH3)]XNHCH2CH2CH2NH2 where x = 2 to 40 ` and : (II) CH2(ocH2lH)xNHcH2cH2cH2NH2 : l c~3 R-CCH2 (0CH2fH) yNlICH2CH2CH2NH2 ¦ CH3 CH2 (CH2fH) z NHCH2CH2CH2NE~2 ; CH3 where x + y ~ z = 3 to 40 ~ and ~ 20 . f f fH3 ( I) H2NCX2CH2CH2HNC~CH2(0~HCH2)X(OCH2CH2) (OCH2CH) 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 f "
: at least one reactive nuclear position available for substitu-,~., tion (o or ~.). Examples: o-, m-, p-cresol, resorcinol, pyrocatechol, hydroquinone, phloroglucinol, pyrogallol,~and : 30 ~ -naphthol, p-tert-butylphenol, 4,4'-dihydroxydiphenylmethane, 4,4'-dihy~roxydiphenylether, 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-, CH3-, C2H5-C4Hg or ~
The preparation of the condensation product is per-formed 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 (~100C) for 1-2 hours and then cooled to ~50C. Amine (aminoalkylene deriva-tive of polyoxyalkylenepolyamines~ addition is begun while -~ raising the temperature to about 165C while water is removed.
Water is removed until overhead temperature drop is notedO
The product is then vacuum stripped at 150C/30mm for 2-4 hours.
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 ad-vantageous to use up to 10 percent excess of the accelerated hardener over the stoichiometric amount.
The curing temperature range of the ambient tem-peratures are rom about 0 to about 45C. Post cures at temperatures up to about 200C are optional. The cured epoxy resins of the invention are useful in castings, coatings, ad-~; hesives, laminates, filament-reinforced composites, seamless flooring, terrazzo flooring, crushed-stone aggregates and in ~6~3~;
grouting, caulking and sealing compositions.
EXAMPLE I. ACCELERATION OF CURE THROUGH USE OF PHENOL-FORMALDEHYDE CONDENSATE OF AN AMINOALKYLENE
DERIVATIVE OF A POLYOXYALKYLENEPOLYAMINE
Formulation: A _ C D
Epoxy resin (EEW 190) 100 100 100 100 JEFFAMINE~ D-400 Bis(propylamine)* 46 - - -JEFFAMINE ~-400 BPA**-Phenol-Formaldehyde Condensate - 52 JEFFAMINE D-230 Bis~propylamine) - - 30 JEFFAMINE D-230 BPA-Phenol-Formaldehyde Condensate - - 38 ~ Gel time, mins. (200 g. mass) 160.3 92.4 73.5 30.8 ; Peak Exotherm, C 160.0 126.5 224.0 213.0 Time to peak, mins. 178.0 114.0 85.0 43.0 *Products of formula I
JEFFAMINE D-400 is a polyoxypropylenepolyamine of formula I
with a molecular weight of about 400.
JEFFAMINE D-230 is a polyoxypropylenepolyamine of formula I
with a molecular weight of about 230.
**Aminopropylene derivatives o JEFFAMINE D-400 : ;
EXAMPLE 2. DEVELOPMENT OF ADHESION: CURING WIT~ PHENOL
~:~ FORMALDEHYDE CONDENSATE VS. JEFFAMINE D-230 BPA
Formulation: A B
Epoxy resin ~EEW 185~ 100 100 ~- JEFFAMINE D-230 Bis(propylamine) 30 JEFFAMINE D-230 BPA Phenol Formaldehyde Condensate - 38 Tensile shear strength, psi after curing for: 4 hours <5 0 ~`~ 8 hours 900 1100 16 hours 2200 2900 ~ 24 hours 1200 3000 : 30 _5_ i3~
EX~MPLE 3. COMPARISON OF CONDENSATION PRODUCT OF THIS
INVENTION WITH SIMILAR CONDENSATE USING POLYOXYPROPYLENE~MINES
Comparison of Properties: Curing with JEFFAMINE D 400; D-400-Phenol-formaldehyde Condensate and BPA D-400-Phenol-formalde-hyde Condensate _rmulation: A B C
Epoxy resin (EEW 185)100 100 100 D-40G Phenol CH2O Cond. - 75 BPAD-400 Phenol CH20 Cond. - - 55 Brook. visc., cps., R.T. 500 3800 4700 Gel time, mins (200 g. mass)~300 142 28.3 Peak exotherm, C. - 71.5 164.0 Time to peak temp., mins. - 180 38.0 Drying time, 6-mil film Set-to-touch, hrs.13.32) 9.9 4.0 Thru-dry, hrs. 15.2 13.2 5.0 ; Rev. impact, in-lbs to fail cure: 24 hr., R.T.>160 148 ~160 7 day, R.T.>160 12 20 ,~ 14 day, R.T.~160 100 100 Proper~ies of cured 1/8" castinqs l) Izod impact strength, ft-lbs~in. 0.52 0.97 0.94 Tensile strength, psi8200 9100 9300 ~ 25 Tensile modulus, psi399000456000438000 :~ Elongation at break, ~3.7 4.6 6.0 Flexural strength, psi1220013200 14200 Flexural modulus, psi400000447000457000 - HDT,C., 264 psi/66 psi41.5/4246/5056/S9 Shore-D hardness, 0-10 sec. 80-77 84-82 86-85 ~L31.~L1633~r % wt~ gain, 1 hr. acetone boil - 13.67 5.36 % wt. gain, 24 hr. H2O boil - 2.34 2.94 )Cured 2 hrs. 80, 3 hrs. 125C
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 appli-cations. In order to provide a rate of cure which is satis-factory ~or 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 Boo~ 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.
; 15 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. Patent No~ 3,639,928 claims the use of a combination of N-(3-aminopropyl)piperazine and salicylic acid as an accelerator comblnation with polyoxyalkylenepoly-amine fox curing epoxy resins.
U.S. Patent 3,734,965 describes the use of a condensation produc~ of phenols, aldehydes and polyoxy-propyleneamines.
:, SUMMARY OF THE INVENTION
The invention i~ 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 con-densation product of phenol, formaldehyde and an ~ ".
,.j:
:, . .
,~
aminoalkylene derivative of a polyoxyalkylenepolyamine. Thus, in its broad-est aspect the invention provides a process for curing epoxy resins comp-rising mixing an epoxy resin in about stoichiometric amounts with a conden-sation product of a phenolic compound, an aldehyde and an aminoalkylene derivative of a polyoxyalkylenepolyaml.ne made by reacting a polyoxyalkylene-polyamine with acrylonitrile followed by hydrogenation. 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 poly-glycidyl 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-hydro-xyphenyl) 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, pdlyoxypropylenepolyamines used as starting materials include compounds of the following formulae:
2NcH(cH3)cH2~oc~2cH(cH3)~xNH2 where x = 2 to 40 and (II) CH2(0CH2CIH)XNH2 ¦ CH3 R-C~H2 (0CH2CIH)yNH2 ~- ¦ CH3 CH2(0CH2lH)ZNH2 ~6336 where x + y + z = 3 to 40 and (III) H2NCHCH2(0CHCH2)x(OCH2CH2)y( 2 z 2 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:
NCH2CH2CH2HNCH(CH3)CH2[OCH2CH(CH3)]XNHCH2CH2CH2NH2 where x = 2 to 40 ` and : (II) CH2(ocH2lH)xNHcH2cH2cH2NH2 : l c~3 R-CCH2 (0CH2fH) yNlICH2CH2CH2NH2 ¦ CH3 CH2 (CH2fH) z NHCH2CH2CH2NE~2 ; CH3 where x + y ~ z = 3 to 40 ~ and ~ 20 . f f fH3 ( I) H2NCX2CH2CH2HNC~CH2(0~HCH2)X(OCH2CH2) (OCH2CH) 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 f "
: at least one reactive nuclear position available for substitu-,~., tion (o or ~.). Examples: o-, m-, p-cresol, resorcinol, pyrocatechol, hydroquinone, phloroglucinol, pyrogallol,~and : 30 ~ -naphthol, p-tert-butylphenol, 4,4'-dihydroxydiphenylmethane, 4,4'-dihy~roxydiphenylether, 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-, CH3-, C2H5-C4Hg or ~
The preparation of the condensation product is per-formed 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 (~100C) for 1-2 hours and then cooled to ~50C. Amine (aminoalkylene deriva-tive of polyoxyalkylenepolyamines~ addition is begun while -~ raising the temperature to about 165C while water is removed.
Water is removed until overhead temperature drop is notedO
The product is then vacuum stripped at 150C/30mm for 2-4 hours.
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 ad-vantageous to use up to 10 percent excess of the accelerated hardener over the stoichiometric amount.
The curing temperature range of the ambient tem-peratures are rom about 0 to about 45C. Post cures at temperatures up to about 200C are optional. The cured epoxy resins of the invention are useful in castings, coatings, ad-~; hesives, laminates, filament-reinforced composites, seamless flooring, terrazzo flooring, crushed-stone aggregates and in ~6~3~;
grouting, caulking and sealing compositions.
EXAMPLE I. ACCELERATION OF CURE THROUGH USE OF PHENOL-FORMALDEHYDE CONDENSATE OF AN AMINOALKYLENE
DERIVATIVE OF A POLYOXYALKYLENEPOLYAMINE
Formulation: A _ C D
Epoxy resin (EEW 190) 100 100 100 100 JEFFAMINE~ D-400 Bis(propylamine)* 46 - - -JEFFAMINE ~-400 BPA**-Phenol-Formaldehyde Condensate - 52 JEFFAMINE D-230 Bis~propylamine) - - 30 JEFFAMINE D-230 BPA-Phenol-Formaldehyde Condensate - - 38 ~ Gel time, mins. (200 g. mass) 160.3 92.4 73.5 30.8 ; Peak Exotherm, C 160.0 126.5 224.0 213.0 Time to peak, mins. 178.0 114.0 85.0 43.0 *Products of formula I
JEFFAMINE D-400 is a polyoxypropylenepolyamine of formula I
with a molecular weight of about 400.
JEFFAMINE D-230 is a polyoxypropylenepolyamine of formula I
with a molecular weight of about 230.
**Aminopropylene derivatives o JEFFAMINE D-400 : ;
EXAMPLE 2. DEVELOPMENT OF ADHESION: CURING WIT~ PHENOL
~:~ FORMALDEHYDE CONDENSATE VS. JEFFAMINE D-230 BPA
Formulation: A B
Epoxy resin ~EEW 185~ 100 100 ~- JEFFAMINE D-230 Bis(propylamine) 30 JEFFAMINE D-230 BPA Phenol Formaldehyde Condensate - 38 Tensile shear strength, psi after curing for: 4 hours <5 0 ~`~ 8 hours 900 1100 16 hours 2200 2900 ~ 24 hours 1200 3000 : 30 _5_ i3~
EX~MPLE 3. COMPARISON OF CONDENSATION PRODUCT OF THIS
INVENTION WITH SIMILAR CONDENSATE USING POLYOXYPROPYLENE~MINES
Comparison of Properties: Curing with JEFFAMINE D 400; D-400-Phenol-formaldehyde Condensate and BPA D-400-Phenol-formalde-hyde Condensate _rmulation: A B C
Epoxy resin (EEW 185)100 100 100 D-40G Phenol CH2O Cond. - 75 BPAD-400 Phenol CH20 Cond. - - 55 Brook. visc., cps., R.T. 500 3800 4700 Gel time, mins (200 g. mass)~300 142 28.3 Peak exotherm, C. - 71.5 164.0 Time to peak temp., mins. - 180 38.0 Drying time, 6-mil film Set-to-touch, hrs.13.32) 9.9 4.0 Thru-dry, hrs. 15.2 13.2 5.0 ; Rev. impact, in-lbs to fail cure: 24 hr., R.T.>160 148 ~160 7 day, R.T.>160 12 20 ,~ 14 day, R.T.~160 100 100 Proper~ies of cured 1/8" castinqs l) Izod impact strength, ft-lbs~in. 0.52 0.97 0.94 Tensile strength, psi8200 9100 9300 ~ 25 Tensile modulus, psi399000456000438000 :~ Elongation at break, ~3.7 4.6 6.0 Flexural strength, psi1220013200 14200 Flexural modulus, psi400000447000457000 - HDT,C., 264 psi/66 psi41.5/4246/5056/S9 Shore-D hardness, 0-10 sec. 80-77 84-82 86-85 ~L31.~L1633~r % wt~ gain, 1 hr. acetone boil - 13.67 5.36 % wt. gain, 24 hr. H2O boil - 2.34 2.94 )Cured 2 hrs. 80, 3 hrs. 125C
2)D-400 Concn.=55 phr.
Comparison of Properties: Curing with JEFFP*lINE D-400, D-400 Phenol CH2O Condensate and BAPD-400 Phenol CH2O Condensate (Acc~ Curing, R.T.) Formulation: A B C
Epoxy resin (EEW 185) 100100 100 D-400 Phenol CH2O Cond. - 75 BPAD400 Phenol CH2O Cond. - - 55 Acc. 398 1010 10 3rook. visc., cps., R.T. - 3800 5000 Gel time, mins. (200 g. mass) 41.031.2 14.2 Peak exotherm, C. 163.0164.0194.0 Time to peak, mins. -42.0 19.5 Drying time, 6-mil film Set-to-touch, hrs. 8.36.0 2.0 Thru-dry, hrs. 11.88.8 3.0 Rev. impact, in-lbs to fail Cure: 24 hr., R~T~ >160 >160 >160 24 h~., RoT~
1 hr. 110C. >160>160 80 7 day, R.T. ~16088 20 14 day, R.T. ~160>160 80 Properties of cured 1/8" castings l) Izod impact strenyth, ft-lbs/in. 0.620.88 0.98 Tensile strength, psi. 75007000 9600 Tensile modulus, psi. 388000418000452000 Elongation at break, % 5.120.8 5.0 i336 Flexural strength, psi.9900 lO900 15100 Flexural modulus, psi.335000 336000 451000 HDT, ~C., 264 psi/66 psi 40/42.5 37/39 48/49 Shore D hardness, 0-10 sec. 83-80 82-80 82-80 % wt. gain, 1 hr. aGetone boil -14.40 9.06 wt. gain, 24 hr. H2O boil - 4.67 3.75 )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.
.
Comparison of Properties: Curing with JEFFP*lINE D-400, D-400 Phenol CH2O Condensate and BAPD-400 Phenol CH2O Condensate (Acc~ Curing, R.T.) Formulation: A B C
Epoxy resin (EEW 185) 100100 100 D-400 Phenol CH2O Cond. - 75 BPAD400 Phenol CH2O Cond. - - 55 Acc. 398 1010 10 3rook. visc., cps., R.T. - 3800 5000 Gel time, mins. (200 g. mass) 41.031.2 14.2 Peak exotherm, C. 163.0164.0194.0 Time to peak, mins. -42.0 19.5 Drying time, 6-mil film Set-to-touch, hrs. 8.36.0 2.0 Thru-dry, hrs. 11.88.8 3.0 Rev. impact, in-lbs to fail Cure: 24 hr., R~T~ >160 >160 >160 24 h~., RoT~
1 hr. 110C. >160>160 80 7 day, R.T. ~16088 20 14 day, R.T. ~160>160 80 Properties of cured 1/8" castings l) Izod impact strenyth, ft-lbs/in. 0.620.88 0.98 Tensile strength, psi. 75007000 9600 Tensile modulus, psi. 388000418000452000 Elongation at break, % 5.120.8 5.0 i336 Flexural strength, psi.9900 lO900 15100 Flexural modulus, psi.335000 336000 451000 HDT, ~C., 264 psi/66 psi 40/42.5 37/39 48/49 Shore D hardness, 0-10 sec. 83-80 82-80 82-80 % wt. gain, 1 hr. aGetone boil -14.40 9.06 wt. gain, 24 hr. H2O boil - 4.67 3.75 )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 (13)
1. A process for curing epoxy resins comprising mixing an epoxy resin in about stoichiometric amounts with a condensation product of phenol, formaldehyde and an aminoalkylene derivative of a polyoxyalkylenepoly-amine made by reacting a polyoxyalkylenepolyamine with acrylonitrile followed by hydrogenation.
2. A process as in Claim 1 wherein the curing takes place from about 0°C to about 45°C.
3. A process as in Claim 2 wherein a post cure is employed at a temperature up to about 200°C.
4. A aprocess as in Claim 1 wherein the amino-alkylene derivative of a polyoxyalkylenepolyamine is an aminopropylene derivative of a polyoxypropylenepolyamine.
5. A process for curing epoxy resins comprising mixing an epoxy resin in about stoichiometric amounts with a condensation product of a phenolic compound, an aldehyde and an aminoalkylene derivative of a polyoxy-alkylenepolyamine made by reacting a polyoxyalkylene-polyamine with acrylonitrile followed by hydrogenation.
6. A process as in Claim 5 wherein the curing takes place from about 0°C to about 45°C.
7. A process as in Claim 6 wherein a post cure is employed at a temperature up to about 200°C.
8. The condensation product of a phenolic com-pound, an aldehyde and an aminoalkylene derivative of a polyoxyalkylenepolyamine made by reacting a polyoxyalkylene-polyamine with acrylonitrile followed by hydrogenation.
9. The condensation product of phenol, formalde-hyde and an aminoalkylene derivative of a polyoxyalkylene-polyamine made by reacting a polyoxyalkylenepolyamine with acrylonitrile followed by hydrogenation.
10. The condensation product of phenol, formalde-hyde and an aminopropylene derivative of a polyoxypropylene-polyamine made by reacting polyoxypropylenepolyamine with acrylonitrile followed by hydrogenation.
11. The condensation product of phenol, formalde-hyde and an aminopropylene derivative of a polyoxypropylene-polyamine of about 400 molecular weight made by reacting polyoxypropylenepolyamine with acrylonitrile followed by hydrogenation.
12. The condensation product of phenol, formalde-hyde and an aminopropylene derivative of a polyoxypropylene-polyamine of about 230 molecular weight made by reacting polyoxypropylenepolyamine with acrylonitrile followed by hydrogenation.
13. A cured epoxy resin composition made by mix-ing an epoxy resin in about stoichiometric amounts with a condensation product of phenol, formaldehyde and an amino-alkylene derivative of a polyoxyalkylenepolyamine made by reacting a polyoxyalkylenepolyamine with acrylonitrile followed by hydrogenation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86505377A | 1977-12-27 | 1977-12-27 | |
| US865,053 | 1977-12-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1116336A true CA1116336A (en) | 1982-01-12 |
Family
ID=25344614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000316369A Expired CA1116336A (en) | 1977-12-27 | 1978-11-16 | Accelerated cure of epoxy resins |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5491598A (en) |
| CA (1) | CA1116336A (en) |
| DE (1) | DE2854827A1 (en) |
| FR (1) | FR2413411A1 (en) |
| GB (1) | GB2011922B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4304889A (en) * | 1980-07-11 | 1981-12-08 | Texaco Inc. | Solvent resistant epoxy coatings |
| JPS59210935A (en) * | 1983-05-17 | 1984-11-29 | Sumitomo Bakelite Co Ltd | Hardener for epoxy resin and blend composition |
| JPS60197723A (en) * | 1984-03-19 | 1985-10-07 | Toray Ind Inc | Composite material |
| US4748167A (en) * | 1984-08-01 | 1988-05-31 | Ppg Industries, Inc. | Water-based coating compositions comprising epoxy-containing acrylic polymers an polyfunctional water-soluble amines |
| JPS61123621A (en) * | 1984-11-20 | 1986-06-11 | Nissan Chem Ind Ltd | Epoxy resin composition for eyeglass frame |
| EP0487188A1 (en) * | 1990-11-19 | 1992-05-27 | Texaco Chemical Company | Alkyl phenol Mannich condensates |
| DE19632749A1 (en) * | 1996-08-14 | 1998-02-19 | Hoechst Ag | Hardening component for epoxy resins and their use |
| KR20040044654A (en) * | 2002-11-21 | 2004-05-31 | 현대자동차주식회사 | Apparatus for operating start motor for engine in automobile and method for controlling said apparatus |
| JP5053582B2 (en) * | 2006-07-10 | 2012-10-17 | 積水化学工業株式会社 | Thermosetting resin, thermosetting composition containing the same, and molded product obtained therefrom |
| EP2452963A1 (en) * | 2010-11-11 | 2012-05-16 | Sika Technology AG | Condensation products of aminofunctional polymers |
| CN104628994B (en) * | 2015-01-30 | 2017-04-05 | 刘平 | A kind of full infiltration saltant type grouting material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1951524B2 (en) * | 1968-11-13 | 1975-11-13 | Hoechst Ag, 6000 Frankfurt | Process for the production of moldings and coatings |
-
1978
- 1978-10-05 JP JP12211678A patent/JPS5491598A/en active Granted
- 1978-11-16 CA CA000316369A patent/CA1116336A/en not_active Expired
- 1978-12-13 GB GB7848355A patent/GB2011922B/en not_active Expired
- 1978-12-19 DE DE19782854827 patent/DE2854827A1/en not_active Withdrawn
- 1978-12-22 FR FR7836115A patent/FR2413411A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS623169B2 (en) | 1987-01-23 |
| JPS5491598A (en) | 1979-07-20 |
| FR2413411B1 (en) | 1983-04-22 |
| GB2011922A (en) | 1979-07-18 |
| GB2011922B (en) | 1982-08-04 |
| FR2413411A1 (en) | 1979-07-27 |
| DE2854827A1 (en) | 1979-06-28 |
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| MKEX | Expiry |