CA1102351A - Process for the preparation of 1,4-diaminobutane derivatives - Google Patents
Process for the preparation of 1,4-diaminobutane derivativesInfo
- Publication number
- CA1102351A CA1102351A CA292,713A CA292713A CA1102351A CA 1102351 A CA1102351 A CA 1102351A CA 292713 A CA292713 A CA 292713A CA 1102351 A CA1102351 A CA 1102351A
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- Prior art keywords
- formula
- diaminobutane
- atoms
- epoxide
- alkyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/54—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
- C07C217/56—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms
- C07C217/62—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms linked by carbon chains having at least three carbon atoms between the amino groups and the six-membered aromatic ring or the condensed ring system containing that ring
-
- 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
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Resins (AREA)
Abstract
Abstract of the Disclosure 1,4-Diaminobutanes of the formula , in which R1 is H or -CH3 and R2 and R3 independently of one another are each a radical of the formula or in which A is alkyl having 1 to 3 C atoms, -OCH3, -N(CH3)2, -Cl or -Br and R2 also is alkyl having 1 to 3 C atoms, are prepared according to the invention by catalytically hydrogen-ating succinic acid dinitrile of the formula
Description
~23~ .
The invention rela-tes to -the preparation of substituted 1,4-diaminobutanes and the use of these compounds as curing agents for epoxide resins.
1,4-Diaminobu-tanes o~ this type are men-tioned in a publica-tion by H. Schafer in Angew. Chemie 82 (1970) 134 as analysis products obtained in a small amount. In the case of the preparation described in this publication, for example, a mixture of a-methylstyrene, glacial acetic acid and sodium azide is subjected to electrolysis. This results in the formation of 1,4-diazido-2,3-dimethyl-2,3-diphenylbutane, with the evolution of a small amoun-t of nitrogen. After the product has been separated off, it can be catalytically hydro-genated in solution to give 1,4-diamino-2,3-dimethyl-2,3-di-phenylbutane.
This process of the state of -the art, which is intended only for analysis, has, however, the serious disadvantage that azides, which, as is known, are explosive products, are obtained as intermediates. Moreover, the yield from thls process is relatively low.
The subject o~ the present invention is a process fo~
the preparation of 1,4-diaminobutanes of the general formula I
: .
~1 (I)
The invention rela-tes to -the preparation of substituted 1,4-diaminobutanes and the use of these compounds as curing agents for epoxide resins.
1,4-Diaminobu-tanes o~ this type are men-tioned in a publica-tion by H. Schafer in Angew. Chemie 82 (1970) 134 as analysis products obtained in a small amount. In the case of the preparation described in this publication, for example, a mixture of a-methylstyrene, glacial acetic acid and sodium azide is subjected to electrolysis. This results in the formation of 1,4-diazido-2,3-dimethyl-2,3-diphenylbutane, with the evolution of a small amoun-t of nitrogen. After the product has been separated off, it can be catalytically hydro-genated in solution to give 1,4-diamino-2,3-dimethyl-2,3-di-phenylbutane.
This process of the state of -the art, which is intended only for analysis, has, however, the serious disadvantage that azides, which, as is known, are explosive products, are obtained as intermediates. Moreover, the yield from thls process is relatively low.
The subject o~ the present invention is a process fo~
the preparation of 1,4-diaminobutanes of the general formula I
: .
~1 (I)
2 2 ~2 R3 2 2 in which Rl is H or -CH3 and R2 and R3 independently of one another are each a radical of the ~ormula ~, _ .
~ ~ A
in which A is alkyl having 1 to 3 C atoms, -OCH3, -N(CH3)2, -C:L or -Br 9 and R is also alkyl having 1 -to 3 C atoms, wherein first a) a succ1nic acid dinitrile of -the formula II
R
NC - C - CH ~ CN (II) ~2 l3 is ca-talytically hydrogenated at temperatures of 20 -to 150C
in the presence of acetic anhydride and, if desired, of addi- :
.:
tional inert organic solvents, then b) the N,N'-diacetyl-1,4- :
diaminobu-tane obtained by the hydrogenation is subjected, after isolation if desired, to acid or alkaline hydrolysis in~an aqueous medium and, finally, c) the 1,4-diaminobutane of the formuIa I is isolated either .in the ~orm of a salt or, after neutralisation with alkali, in the form of the ~ree base.
A succinic acid dinitrile of the ~ormula II in which Rl is H or -CH3, R2 is one of the radicals CH
~ C1 ~ H3 and alkyl having up to 3 C atoms and R3 is one of -the radicals ~ ~ Cl and ~ 0 CH3 it being possible for R2 and R3 to be iden-tical or difXerent, is preferably used in the process according to -the invention.
In a par-tlcular embodiment of the process according to :' ,, ~
-the invention, a succinic acicl dinitrile of the formula II is employed in which Rl is H and R2 and R3 are each a radical of the formula ~ or ~ ~
in which A is alkyl having 1 to 3 C a-toms, preferably -CH3, or -OCH3, -N(CH~)2, -Cl or -Br, preferably -Cl.
The substituted N,N'-diacetyl-1,4-diaminobutane obtained as an intermediate in the process according to the invention is of the formula IV
CH3.CO.HN - CH~ - C CH _ CH2 - NH.CO.CH3 (IV) . R2 R3~ .
. ; ;~ . :
in which Rl, R2 and R3 are as~defined in formula II. The N,N'-diacetyl derivatives of the :Eormula IV haYe not yet been ~ -described in the literature and are thus valuable starting compounds for the preparation of -the 1,4-diaminobutanes of -the ~
formula I. - -A succinic acid dinitrile of the formula II which is particularly preferentially employed is a succinic acid di-nitrile of the formula III
NC CH CH - CN
~ ~ (III) This product can be prepared, for example, by reacting banz-aldehyde, benzyl cyanide and sodium cyanide. Other di-nitriles of the formula II which are -to be used as starting . :
~ ~ A
in which A is alkyl having 1 to 3 C atoms, -OCH3, -N(CH3)2, -C:L or -Br 9 and R is also alkyl having 1 -to 3 C atoms, wherein first a) a succ1nic acid dinitrile of -the formula II
R
NC - C - CH ~ CN (II) ~2 l3 is ca-talytically hydrogenated at temperatures of 20 -to 150C
in the presence of acetic anhydride and, if desired, of addi- :
.:
tional inert organic solvents, then b) the N,N'-diacetyl-1,4- :
diaminobu-tane obtained by the hydrogenation is subjected, after isolation if desired, to acid or alkaline hydrolysis in~an aqueous medium and, finally, c) the 1,4-diaminobutane of the formuIa I is isolated either .in the ~orm of a salt or, after neutralisation with alkali, in the form of the ~ree base.
A succinic acid dinitrile of the ~ormula II in which Rl is H or -CH3, R2 is one of the radicals CH
~ C1 ~ H3 and alkyl having up to 3 C atoms and R3 is one of -the radicals ~ ~ Cl and ~ 0 CH3 it being possible for R2 and R3 to be iden-tical or difXerent, is preferably used in the process according to -the invention.
In a par-tlcular embodiment of the process according to :' ,, ~
-the invention, a succinic acicl dinitrile of the formula II is employed in which Rl is H and R2 and R3 are each a radical of the formula ~ or ~ ~
in which A is alkyl having 1 to 3 C a-toms, preferably -CH3, or -OCH3, -N(CH~)2, -Cl or -Br, preferably -Cl.
The substituted N,N'-diacetyl-1,4-diaminobutane obtained as an intermediate in the process according to the invention is of the formula IV
CH3.CO.HN - CH~ - C CH _ CH2 - NH.CO.CH3 (IV) . R2 R3~ .
. ; ;~ . :
in which Rl, R2 and R3 are as~defined in formula II. The N,N'-diacetyl derivatives of the :Eormula IV haYe not yet been ~ -described in the literature and are thus valuable starting compounds for the preparation of -the 1,4-diaminobutanes of -the ~
formula I. - -A succinic acid dinitrile of the formula II which is particularly preferentially employed is a succinic acid di-nitrile of the formula III
NC CH CH - CN
~ ~ (III) This product can be prepared, for example, by reacting banz-aldehyde, benzyl cyanide and sodium cyanide. Other di-nitriles of the formula II which are -to be used as starting . :
3~i~
materials for the process according to the invention can also be prepared correspondingly. More precise information on the reac-tion is -to be ~ound in the publication by R.B. Davis in J. Amer. Chem. Soc. 80 (1958) 1,752. All of the di-nitriles lis-ted in Table I in this publica-tion can be employed as s-tarting ma-terials ~or the process according to the inven-tion. Other dini-triles not mentioned in Table I can, of course, also be employed if they correspond to the formula II.
The temperature suitable for the hydrogenation accord-ing to stage a) is in each case dependent on -the hydrogena-tion catalyst used. If Raney nickel or Raney cobalt is used, the reaction condi-tions are op-timum, in respect of the yield, when tempera-tures of about 90 to 1~0C are used. When known noble metal catalysts, such as platinum, palladium, rhodium or ruthenium, are employed, the reaction can be carried out at lower temperatures, such as, say, at room temperature.
The hydrogenation can be carried out by the methods customary in the laboratory and in industry, either under normal pressure, for example in a duck-shaped shaking vessel, or under pressure in an autoclave.
Additional inert organic solvents which can be used for the hydrogenation are, for example, hydrocarbons or ethers, such as hexane and dioxane, or aroma-tic compounds, such as toluene or benzene.
The catalytic ~eduction is as a rule carried out by mixing a solution of the particular succinic acid dinitrile of the formula II in acetic anhydride and, if desired, a solvent ~..,;
with the ca-talyst and passing hydrogen gas into the reaction mix-ture. The hydrogenation is continued ~mtil no further hydrogen is absorbed. The catalyst is then separated off.
In -the second stage b), the resul-ting subs-tituted N,N' diacetyl-1,4-diaminobutane is generally firs-t isolated and then subjected to acid or alkaline hydrolysis. In principle~ however, -the hydrolysis can also be carried out withou-t separating OI'f the diace-tyl compound, i.e. direct in the solution, which has been freed from the catalyst, and is ob-tained from stagea)~ The intermediate is isolated by known pro-cesses.
The acyla-ting hydrogenation in -the presence of acetic anhydride employed in stage a) of the process according to the invention is known per se but in the present case ultimately ~ -results in solid, substituted 1,4-diaminobutanes which, sur- --prisingly, are outs-tandingly sultable as curing agents ~or epoxide resins in respect of po-t life, colour s-tability and stability to aggressive media, especially organic acids and alcohols, and some of which are even superior to some con-~entional curing agents. This is the case, in particular, for adduct curing agents obtained from the substituted 1,4-diaminobu-tanes,which can be prepared by the process according to the invention,and liquid polyepoxide compounds.
The 1,4-diaminobutanes of the ~ormula I which can be prepared according to the invention are also particularly suitable for the production of pre-reaction products with epoxide resins (B-stages). For the preparation o~ such - 6 ~
, 3~3L
R-stages, as is known, the corresponding epoxide resin is mixed with the curing agent and the mixture is stored either at room temperature for about 1 to 14 days or at slightly elevated temperature (not higher than 60C) for one or se~eral hours. The B-stages which form during'this storage are : .
u~ed, a~ nown, lnter alia ~ compre3~isn mouldlng compo-sitions, pre-pregs for laminates, sintering powders a~d adhesives. Those based on the 1,4-diaminobutanes of the formula I which can be prepared according to the invention are suprisingly superior to the conventional B~stages which, as is known, contain predominantly aro~atic amines as the ouring agents. This superiority is particularly surprising because the basic character of the 1,4-diaminobutanes o~ the formula I is rather that of aliphatic amines. However, as is known, aliphatic amines are unsuitable in practice for the preparation of B-stages~
The invention further also re:Lates to cura~le mlxtures containing a 1,4-diaminobutane o~ the formula I and a poly-epoxide compound (designated X here) having, on a~erage, more than one epoxide group in the molecule, there being9 in the mixtures, 0.5 to 1.5 equivalents o~ active hydrogen atoms, bonded to nitrogen,.in the particular 1,4-diaminobutane per 1 equivalent of epoxide groups in the epoxide compound (X).
A preferred form of the curable mixtures accordi~g to the invention comprises those which contain the 1,4-diamino-butane of the formula I in the form of an adduct curing agent (E) having an amine number of 4.0 to 4.7 ob-tained from the ~ diaminobutane of the formula I and a liquid epoxide com-pound (designa-ted Z here) having, on average, more -than one epoxide group in the molecule and, if desired, phenylglycide.
In such mixtures there are 0.8 -to 1.2 e~uivalents of active hydrogen atoms bonded to the nitrogen atoms ol the adduct curing agen-t (E) per l equivalent of epoxide groups in the epoxide compound (X). Bisphenol A epoxide resins or bis-phenol F epoxide resins are preferably employed as liquid epoxide compounds (Z) for the preparation of the adduct curing agen-ts (E). The preparation of the adduct curing agents (~) is preferably effected by warrning a mixture of a 1,4-diaminobutane of the forrnula I, an epoxide compound (Z) and, if desired, phenylglycide (molar ra-tio: l.0 : 0.13 : 0.2) to temperatures of 12GC to 200C.
The adduct curing agent (E) can additionally also con-tain 5 to 10% by weight, relative -to the pure adduct curing agent, of salicylic acid as a reaction accelerator.
The invention further also relates to the B-stages which are stable on storage and have already been described and which are to be regarded as a preferred form of -the curable mixtures according -to the invention.
Polyepoxide compounds (X) which can be used for the curable mixtures according to the invention are~ in particular, those having on average more than one glycidyl group, ~-methyl-' ' ', .
315~ :
glycidyl group or 2,3-epoxycyclopentyl group bonded to a -:
hetero-atom (for example sulphur and preferably oxygen or nitrogen~; preferred compounds are bis-(2,3~epoxycyclo-pen-tyl) e-ther; di- or poly-glycidyl ethers of polyhydric aliphatic alcohols, such as 1,4-butanediol, or polyalkylene glycols~ such as polypropylene glycols; di- or poly-glycidyl -ethers of cycloaliphatic polyols, such as 2,2-bis-(4-hydroxy-cyclohexy].)-propane; di- or poly-glycidyl e-thers of poly-hydric phenols, such as resorcinol, bis-(p-hydroxyphenyl)-methane, 2,2-bis-(p-hydroxyphenyl)-propane (= di~methane), 2,2~bis-(4~-hydroxy-3~,5 t -dibromophenyl)-propane, 1,1,2,2-tetrakis-(p-hydro~yphenyl)-ethane or of condensation products of phenols with formaldehyde obtained under acid conditions, such as phenol novolacs and cresol novolacs; di- or poly- -~
(~-methylglycidyl) ethers of the abovementioned polyhydric alcohols or polyhydric phenols; polyglycidyl esters o~ poly-basic carboxylic acids, such as phthalie acid, tereph-thalic acid~ ~4-tetrahydrophthalic acid and he~ahydrophthalic acid;
N-glycidyl derivatives o~ amines, amides and heteroeyeIie nitrogen bases, such as N,N-diglycidyl-aniline, N,N-diglycidyl-toluidine and N,N,N',N~-tetraglyeidyl-bis-(p-aminophenyl)-methane; triglycidyl isocyanùrate; N,N'-diglycidylethylene-urea; N,N'-diglycidyl-5,5~dimethyl-hydantoin and N,N'-di-glycidyl-5-isopropyl-hydantoin; and N,N'-diglycidyl-5,5-dimethyl-6-isopropyl-5,6-dihydro-uracil.
I~ desired, active diluents, for example styrene oxide, ; butyl glyeidyl ether, isooctyl glycidyl ether, phenyl glyeidyl : - ~ ' , ', ';, ~2~
ether~ cresyl glycidyl ether or glycidyl esters of synthetic, highly branched, mainly -tertiary aliphatic monocarboxylic acids ("CARDUR~ E"), can be added to the polyepoxides in order to lower the viscosity.
The curing of the curable mixtures according to the invention -to give mouldings and the like is carried out in the temperature range of 20 to 160C when the free 1,4-diamino-butanes of the formula I are used. However, if the mix---tures contain the described adduct curing agents of -the 1,4- -diaminobutanes, curing is preferably carried out at tempera-tures of 5 to 250C.
In order to shorten the gelling times or curing -times, known accelerators for the amine curing reaction, for example monophenols or polyphenols, such as phenol or dlomethane, salicylic acid, tertiary amines or salts of thiocyanic acid, such as NH4SCN, can be added.
Furthermore, conventional modifiers, such as ex-tenders, fillers and reinforcing agents, pigments 9 dyes, organic sol-vents, plasticisers, flow control agents, agents for conferring thixotropy, ~lameproofing agents and mould release agents, can be added to the curable mix-tures, according to the invention, of polyepoxide compounds (X) and 1,4-diaminobu-tanes of the formula (I) or corresponding adduct curing agents in any stage before curing.
The following may be mentioned as examples of extenders, reinforcing agents, fillers and pigments which can be employed in the curable mixtures according to the invention: coal tar, _j :.. , ~ . .
., .
351 :`
bi-tumen, liquid coumarone-indene resins, -textile fibres, glass fibres, asbes-tos fibres, boron ~ibres, carbon fibres, cellu-lose, polyethylene powders and polypropylene powders; quartz powder; mineral silicates, such as mica, asbestos powder or slate powder; kaolin, aluminium oxide trihydrate, chalk powder, gypsum, antimony trioxide, bentones, silica aerogel ~"AEROSIL"), lithopones 9 baryte, -titanium dioxide, carbon black, graphite, oxide colours, such as iron oxide, or metal powders, such as aluminium powder or iron powder.
Suitable organic solvents for modifying the curable mixtures are, for example, toluene, xylene, n-propanol, butyl acetate, acetone, methyl ethyl ketone, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether.
Examples o~ plasticisers which can be employed for ~-modi~ying -the curable mixtures are dibutyl phthalate, dioctyl ;-phthalate and dinonyl phthalate, tricresyl phosphate, trixyl-enyl phosphate, diphenoxyethylformal and polypropylene glycols.
These plasticisers can also already be constituents o~ the curing agent, especially of the adduct curing agent. In such cases, the plasticisers are present in a concentration of 25 to 50/O by weight, relative`to the pure curing agent.
Examples of ~low control agents whioh can be added when the curable mixtures are employed particu]arly in surface protection are silicones, liquid acrylic resins, cellulose acetobutyrate, polyvinylbutyral, waxes, stearates and the like (some of which are also used as mould release agen-ts).
3~
Particularly for use in the lacquer field, the poly-epoxide compounds can furthermore be partially esterified in a known manner with carboxylic acids, such as, in particular~
hlgher unsa~urated fat-ty acids. It is also possible -to add o-ther curable synthetic resins, for example phenoplasts or aminoplasts, to such lacquer resin formulations.
The curable mixtures according to the invention can be produced in a conventional manner with the aid of known mixing equipment (stirrers, kneaders, rolls, or, in the case of solid powders, mills or dry mixers).
The curable epoxide resin mixtures according to the invention are employed in particular in the flelds of surface protection, -the electrical industry, laminating processes and adhesives technology and in -the building trade. They can be used in a formulation suited ln each case to the particular application, in the unfilled or filled state, if appropriate in the form of solutions or emulsions, as paints, lacquers and solvent-free coatings, as sintering powders, compression moulding compositions~ injection moulding formulations, dipping resins, casting resins, impregna-ting resins, binders and adhe-sives and as tool resins, laminating resins, sealing and filling compositions, floor covering compositions and binders for mineral aggregates.
Example 1 Precursor: N,N'-Diacetyl-1,4-diamino-2,3 diphenylbutane 34.9 g (0.15 mol) of 2,3-diphenyl-succinic acid , ~
. ''' 3~.
dinitri:Le are hydrogena-te~ at 120-125C and under a pressure of 120 atmospheres gauge in 200 ml of toluene and 35.3 g (0.36 mol) o~ acetic anhydride in an autoclave in the pre-sence of 3.5 g of Raney nickel. me absorption of H2 has ceased after 30 minutes and N,N'-diace-tyl-1,4-diamino-2,3-phenylbutane crys-tallises ou-t on cooling. The super-natant solution is decanted off and the residue is boiled wi-th 300 ml of ethanol~ whereupon the produc-t dissolves.
In order to separate of~ the catalyst, the mixture is fil-tered ho-t and the filtrate is partially concentrated. The product then crystallises ou-t and is filtered off a-t room temperature, washed with ethanol and dried a-t 80C. Yield:
30,5 g; melting point: 221-222C. A further 3.4 g of substance are obtained by concentrating, so tha-t the total yield is 33.9 g (69.5% of -theory). For analysis, 1 g is recrystallised from 10 ml of ethanol. Yield: 0.8 g;
melting point 221-222C.
Analysis C20H24N2o2 (molecular weight = 324.41) - calculated C 74.04 H 7.46 N 8.64 ~- found C 74.11 H 7.58 N 8.68 The NMR spectrum agrees with the structure.
1, 4-Diamino~,3~ph~1butanè
385.7 g (1.19 mols~ of N,N'-diacetyl-2,3-diphenyl-1,4-diaminobutane in 715 ml of 5N sodium hydroxide solution are heated to 200C in an autoclave for 16 hours. After cooling, the mixture is extracted with 1,800 ml of chloroform.
Further extraction with 2 times 200 ml of chloroform and concentration of the extrac-ts gives 285.4 g of crude product, which is recrystallised from 2.6 1 of benzene. Yield:
258.5 g of 1,4~diamino-2,3-diphenylbu-tane; melting point:
144-145C. A fur-ther 15.1 g of substance having a melting point of 144-145C are obtained by concentrating the mother liquor; -the total yield is thus 273.6 g (95.7% of ~theory).
For analysis, 1.0 g is recrystallised from 10 ml of benzene.
Yield: 0.88 g; melting poin-t: 144~145C; meso ~orm.
Analysis Cl~H20N2 (molecular weight = 240.34) calculated C 79.95 H 8.39 N 11.66 found C 79.88 I-I 8.31 N 11.69 The NMR spectrum agrees with the structure.
Example 2 Precursor: N,N' Diacetyl 1,4-diamino-2-(p-chlorophenyl)-3-(p-methoxyphenyl)_butane.
29.6 g (0.10 mol) of Z-(p-chlorophenyl)-3-(p-methoxy-phenyl)-succinic acid dinitrile are hydrogenated for 4 hours at 110C and under a pressure of 100 atmospheres gauge in 200 ml of toluene and 25 g (0.24 mol) of acetic anhydride in an autoclave in the presence of 3 g of Raney nickel. The -totàr-reaotion mixture is then concentrated in a rotary evapo-rator, the residue is boiled ùp with 700 ml of ethanol and the Raney nickel is filtered off. After concentrating the fil-trate to 200 ml, the product crys-tallises out. After filtering off, washing and drying, 19.0 g (48.8% of theory) of a substance having a melting point of 235-238C are obtained.
The filtrate is completely evaporated in a rotary e~aporator;
~Z3~
recrystallisa-tion of the residue ~rom 100 ml of ethanol gives a fur-ther 2.3 g of produc-t having a melting poin-t of 232-236C.
To-tal yield: Z1.3 g (54.7% of theory).
1?4-Diamino 2~ chl~x~hen~])-3-~p-methoxy~henyl)-butane , .
21.14 g (0.054 mol) of N,N'-diacetyl-1,4-diamino-2-(p-chloroFhenyl)-3-(p-methoxyphenyl)-bu-tane in 80 ml of 15%
s-treng-th aqueous sodium hydroxide solution are heated to 200C
in an autoclave for 12 hours. Af-ter cooling, the mixture is extrac-ted with chloroform and the organic phase is washed with water and then evaporated in a rotary evaporator.
Yield of crude product: 13.2 g (79.6% of theory) of a crystalline product. For purification, this product is recrystallised ~rom 200 ml o~ cyclohexane, then filtered of~, washed with cvclohexane and dried in vacuo at 60C. Yield:
~,, 11.55 g (69.6% of theory~; melting point: 124-127C.
Analysis C17H21N20Cl (mQlecular weight = 304.82) calculated C 66.99 H 6~94 N 9.19 found C 67.06 H 6.87 N 9.09 ~ ' .
Precursor: N,N'-Diacetyl-1,4 diamino-2-p-tolyl-3-phenyl butane.
24.6 g (0.10 mol) of 2-p-tolyl-3-phenyl-succinic acid dinitrile are hydrogena-ted at`l20C and under 100 atmospheres gauge in 250 ml of toluene and 31 g (0.30 mol) of acetic anhydride in an autoclave in the presence of 2.5 g of Raney nickel until a constant pressure is reached. The total mixture is concentra-ted to about 100 ml in a rotary evaporator, 600 ml of ethanol are added, the mixture is heated to the - 15 ~
2;3S3L
reflux temperature and the ca-talys-t is filtered off hot.
Af-ter concen-trating the flltra-te to about 300 ml, -the product crystallises out on cooling in a refrigerator. Yield:
18.5 g (54~6% of theory); melting po~nt: 226-7C. A
fur-ther 3.0 g (8.9% of theory) of produc-t having a melting point of 222-6C are ob-tained by concen-tra-ting the mother liquor. Recrystallisation of 0.80 g of the ~irst frac-tion from 12 ml of e-thanol gives 0.49 g of pure product having a melting point of 226-7C.
~nalysis C21H26N202 (molecular weight = 338.45) calculated C 74.53 H 7074 N 8.28 found C 74.39 H 7-71 N 8.49.
~ i! 18.6 g of N,N~-diacetyl-1,4-diamino-2-p-tolyl-3-phenyl-butane in 80 ml of 15% strength aqùeous sodium hydroxide solu-tion-are heated to 200C in an au-toclave for 16 hours~ On concentrating the solution, the amine partially crystallises out. The mixture is extracted 3 times with 50 ml of chloroform and after evaporating the extracts in a rotary evaporator 13.8 g of crystalline crude amine are obtained.
Recrystallisation from 110 ml of cyclohexane gives 12.2 g (87.3% of theory) of diamine having a melting point of 112-14C.
Analysis C17H22N2 (molecular weight = 254.38 calculated C 80.27 H 8.72 N 11.01 found C 80.05 H8.64 N 11.34.
. ~ , .
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Precursor: N,N'-Diacetyl-1,4-diamino~2-(p-dimethylamino-phenyl)-2-phenyl butane.
13~4 g of 2-(p-dimethylamino-phenyl)-3-phenyl-succinic acid dinitrile are hydrogena-ted a-t 120C and under 100 atmos-pheres gauge in 250 ml of toluene and 15 g of acetic anhydride in an autoclave in the presence of 1.5 g of Raney nickel until constant pressure is reached. The mixture is concentrated to 50 ml, 300 ml of e-thanol are added and J a~ter boiling up, the catalyst is filtered off. All of the solven-ts are then removed in a rotary evaporator and the reside is recry-stallised from 60 ml of acetonitrile. 3.1 g of a product having a melting point of 205-9C are obtained in the first fraction. The NMR spectrum is in agreement with the ~`
structural formula ~ ~ ~ ' 19.1 g of N,N'-diacetyl-1,4-diamino-2-(p-dimethyl aminophenyl)-3-phenyl-butane in 80 ml of 15~ strength aqueous sodi~n hydroxide solution are heated to 200C in an autoclave for 16 hours. The reac-tion solu-tion is then concentrated in a rotary evaporator and extracted with chloroform. After . .
removing the chloroform in vac~o, 8.5 g of crys-talline crude amine are obtained and this is recr-ystallised from 35 ml of isopropanol. Yield: 3.8 g of product having a melting point o~ 145-146C. A further 2.0 g of product having a melting point of 145-146C are obtained by concentrating.
Analysis C18H25N3 ~molecular weight = 283.
;
s~
calculated C 76.28 H 8.90 N 14.8~
found C 76.26 H 8.93 N 14.74.
B) Use Ex~
-(Casting and adhesive resin) 31.8 g of 1,4-diamino-2,3-diphenylbutane are homogen-ised, by means of a triple roll mill, together with ~00 g of a liquid unmodified epoxide resin (X) which is based on bis phenol A and has an epoxide content o~ 5.3 equivalentjkg and a viscosi-ty of 10 9 800 cP/25, a viscous white suspension being obtained.
The following methods are used to determine the various characteristics:
Differential thermal analysis is used to determine -the reactivity. About 20 mg of -the resin/curing agent mixture to be tes-ted are warmed in a small Al crucible in the measuring chamber of a type TA 2000 differential thermoanalyser from Messrs. Mettler (Greifensee, Switzerland) at a heating rate of 4/minute and the temperature difference between this crucible and an empty crucible warmed at the same time is recorded continuously. The temperatures for the start of reaction, for the maximum reaction rate and for the end of the reaction are read off, as parameters characterising the reactivity, ~rom the curve thus obtained. The area under the`curve enables the heat liberated during the reaction to be determined and gives an indication of the completeness of the conversion.
..
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b) Determination of_-the lass transition -temperature '4 g of -the resin/curing agent mix-ture are, in each case, poured in-to a thin-walled Al crucible of about 5 cm diame-ter and cornpletely cured in this crucible (4 hours at 80C and 8 hours at 140C). A sample is -taken from the disc thus obtained in order to determine the glass transition temperature of -the crosslinked polymer with the aid of differ-en-tial thermal analysis. The specific heat changes at the transition point; this change is registered as a turn-ing point in the curve recorded by the DTA apparatus.
Conclusions regarding the dimensional stabili-ty of the result~
ing polymer when ho-t can be drawn from the glass transition tempera-ture.
c) Determination of the mechanical and dielec-tric properties The resin/curing agent mixture prepared as described above is poured into aluminium moulds, which have been pre-treated with mould release agents, in order to produce sheets having dimensions of 135 x 135 x 4 mm and 135 x 1~5 x 2 mm and the sheets are cured for 4 hours at 80C and 8 hours at 140C.
The 4 mm thick sheets~are used to produce test pieces having dimensions of 60 x 10 x 4 mm for determining the flexu-ral strength and deflection according to VSM Standard Specifica-tion 77,103, the impact strength according to VSM
Standard Specification 77~105 and the increase in weight after storage in water.
'' ,, . .. , : ~
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The 2 mm thick sheets are used to determine the diélectric properties.
d~_Test to deter ne the suitabil ty as an adhesive A small amoun-t of the resin/curing agent mixture is applied, in each case, -to the ends of test strips made of anticorodal B which have dimensions of ]70 x 25 x 1.5 mm and have previously been roughened by grinding and degreased by washing with solven-ts. In each case, two of these test strips are so adjusted with -the aid of a gauge that the ends coated wi-th resin/curing agent mixture overlap by 12 mrn.
After fixlng with a clamp, the adhesive is cured and after cooling the clamp is removed and the -tensile shear strength o~ the glue bond is then tested in a tensile test (DIN 53,183~.
~ ::
A small amount of the resin/curing agent suspension is distributed on a sheet of glass by means of a glass rod so that a uniform film is obtained. The coating obtained after curing is tested to determine its chemical stability by leaving a drop o~ the par-ticular chemicals on the film ~or 1 hour. The chemicals are then wiped off and the sur~ace of the film is assessed visually.
The characteristics de*ermined for the various test ?
pieces by the methods mentioned are summarised in Table 1.
EXample I shows -that mixtures of 1,4-diamino-2,3-diphenylbutane and epoxide resins are very reactive and give mouldings with good mechanical and electrical proper-ties and a high glass transition temperature. If the mix-tures are .
'' ~ .
~Z.~
applied in a thin layer in the form of a solven-t-free coa-ting, films are obtained which have very good stability towards solven-ts and aggressive chemicals in aqueous solution.
Mixtures of thls type can also readily be used for glue bonds.
Table 1 (relating to Example I) 100 par-ts of epoxide resin Sys-tem based on bisphenol A
31.8 parts of 1,4-diamino-2,3-diphenylbutane ~ , T~ 2000 TRRmax 102 En-thalpy 20,815 cal/equivalent of epoxide/amine sys-tern Curing 4 hours at 80C
Appearance of -the moulding material whlte, opaque ~ . _ Impact strength (cmkg/cm2) 5-5 Flexural strength (kg/mm2) 9.2 Deflection (mm) 3.2 Glass -transition temperature (C) 151 Absorption o~ H O, 4 days at room tempera-ture2 ~%) 0.29 Absorption of H20, 1 hour in boiling water (%) 0.63 Tensile shear streng-th (kg/mm2~ 1.7 _ Chemical stabili-ty towards .
5N NaOH no attack o~ any type .H20 . de-tectable acetone -Cl-benzene Loss fac-tor tan ~
>1% above 79 ~5% above 104 Dielectric constant at 25C 3.6 Specific volume resistivity 25 (~xcm) 4.7x1016 , LL~
TRRmaX = Temperature a-t the maximum ra-te of reaction TS = Temperature a-t -the star-t of the reaction TE = Tempera-ture a-t the end of the reaction (Solvent-free coating systems) Preparation of the_adduct curin~ a ents Addwct curin~ agent I according -to the invention 50 g of a liquid epoxide resin (Z) based on bisphenol A and having an epoxide equivalent weight of 168 and a vis-cosity of about 37400 cP (25C) are mixed together with 180 g o~ diphenoxyethylformal and 240 g of 1,4-diamino-2,3-diphenyl-butane in a -three-necked flask and the mixture is heated to 150C. 30 g of phenylglycide are then added dropwise and the mixture is reacted at 150-170C for 25 minutes. After cooling to about 120C, 35 g of salicylic acid are melted into the mixture, with stirring. The finished adduct curing agen-t is-discharged at about 50C. Charaoteristics: see Table 20 (as comparison) Base~ on: 4,4' diamino-diphenylmethane.
Table_2 (Charac-teristics of the curing agents according to Example II) . . .. . ~ _~ ~
Curing Viscosi-ty Amine H equivalen-t Suitable mixing agent a-t 25C in number weight ra-tio of epoxide cP (accord- resin to be cured:
ing to adduct curing Ho0ppler) agent . .. ._ ~ ~_... ~ - . .. . . . .~
I ~100,000 4.5 127 100:66 _ _~ _ __ . .
II 6,700 4.5 115 100-60 ~ 23 -,_,, .. , .. . , .,.. ,.. ,,.. , ., ., .... ... ............ , ... ........ ,... , . ... .. ... , -.-P~
A liquid bisphenol A epoxide resin (X) hav:ing a vis- :
cosi-ty of 11~300 cP at 25C and an epoxide equivalent weigh-t of 194 is mixed wi-th -the aclduct curing agent I in a weight ratio of 100:66 (mix-ture I). An analogous mixture is also prepared using the conventional adduct curing agent II (mix-ture II). In both cases, cleaned, 0,8 mm thick steel sheets are coated -to a thickness of 200 ~m (thickness of the wet film) wi-th the mix-tures I and II. These metal sheets are used to de-termine -the properties in respect of lacquer technology and these properties are compared in Table 3. In :
order -to test the stability towards dilute acetic.acid and ::
alcohol, fur-ther steel shèets are coated -to a layer thickness of 300 ~m. The corresponding results are compared in Table L~, ' .
- 24 - ~ -'I ' ~ , ' ' ' ' '" " ' ,;
.
, p~s~
(Proper-ties in respect of lacquer -technology for mixtures I
and II and -the coatings produced) _ Mixture I II
. . . _ , . . , , , _ _ Gel time for 100 ml (Tecam appara-tus) >210 mins. 140 mins.
Viscosity of the mixture (25C) cP ~ 50,000 9,000 Time for drying to -touch¦hours 7 12 Through-curing -time/hours 20 15 Appearance of the film 20/65%
relative humidity good good Appearance of the film 20/100%
relative humidity good good Appearance o~ -the film 5/45%
relati~e humidity . good good Hardness (Persoz) seconds/7 days 320 345 Erichsen ~l/m/7 days 3 - 5 C 2 Impact cmkg 30-40 ~ 40 Adhesion on sand-blasted sheet steel good moderate Stabili-ty to boiling water (6 hours/96C) good good ~ 72 rJ 72 Table 4 __ (Stabili-ty of -the coatings towards dilute acetic acid and ethyl alcohol in months Layer thickness: about 300 ~m on sand-blasted sheet steel, curing 10 days) . _ , _ ~ ~ , _, ~
Mixture I II III IV
_~ ~ __ , _ _ , Acetic acid, 5%~6 ~12 ~12 1 D
. Acetic acid, 10% ~6 ~12 ~ ~ 1 D
Ethanol, 20% ~ ~12 ~7 Ethanol, 50~0 1-6 A 7-9 D C 1 D _ -- . . , , ,~ , ~. ,,."~ __ _ ~ ~
;3S~IL
Legend: 1-6 A signifies: Film a-ttacked, for example softer or formation of bubbles 9 from 1~6 months 1 ~ signi~ies: Film destroyed before 1 month ~6 and ~8 signifies: Film intact after 6 and 8 months respec-tively (test con-tinued) Mixture III containing~ curing agent III = adduct (associate) of 4,4'-diamino-3,3-dimethyl-dicyclohexylmethane and nonylphenol Mixture IV containing: curing agent IV = adduct (associate) of trime-thylhexamethy-lenediamine and nonylphenol.
r~AI~t~~ ~ tb~ l~s~lt~ ~
If the processing charaoteristics, which are very important industrially, and the properties in respect of lacquer technology which are achieved with the coatings are first compared with the aid of Table 3, the curable mlx-ture I
containing the adduct curing agent I based on 1,4-diamino-2,3-diphenylbu-tane has a longer po-t life (of ~210 ~inutes) com-pared with the mixture II containing the adduc-t curing agent II based on 4,4l-diamino-diphènylmethane and this ~acilitates easy processing by hand with a brush and roller, for which there is a great demand in practice.
Some of the other properties in respec-t of lacquer -~
tec~mology of such coatings are superior to the properties of coatings which contain curi.ng agents based on conventional '~.
_ 26 --.. . . . . . . .
.. . . .
~"': ;' ,' : , , : :
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aromatic amines. The colour stability of the novel aclduct curing agent I is significantly be-tter and -this rnakes it possible, for example, to produce whi-te-pigmented coatings.
In respec-t of the stabili-ty to highly aggressive media such as dilute organic acids (5/0 st,rength and 10% strength ace-tic acid) and also 20% and 50% ethyl alcohol, which are a factor de-termining -the quality in the foods-tuffs sec-tor, -the novel adduc-t curing agent I shows up very well when compared with the curing agent based on 4,4'-diaminodiphenylmethane and is distinc-tly superior to the other conventional curing agents based on aliphatic and cycloaliphatic polyamines (compar-ison mixtures III and IV, Table 4).
Example III
(Pre-reaction product which is stable on storage; B-stage) The resin/curing agent mixture described in Example I
and a suspension prepared from 100 parts by weight of -the same epoxide resin ~X) and 26.2 parts by weight of 4,4'-diamino-diphenylmethane, which is intended to enable a comparison to be made with the state of -the art, are stored at room temp-erature (RT) and their reactivity and their softenlng range are checked at specific intervals. Two different experi-mental methods are used for this purpose:
a) Determination of the gel time at 120C on a thermo-statically controlled hot-pla-te and b) Determlnation of the reactivity using the ~ifferential Thermoanalyser already described above.
In addition to changes in the temperatures for the , . .
L
melting point, the star-t of reac-tion and -the reac-tion maximum 7 the de-terminati.on of the hea-t of reaction fur-ther liberated during complete curing of -the pre-reaction products in parti-cular enables an assessment to be made of the degree of conversion be~ore and after s-torage of the pre-reac-tion produc-t.
The values determined ~or the two systems by the methods mentioned are summarised in Tablë 5.
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Evalua-tion of the results _ According to Example III it is surprisingly possible by simply grinding the solid amine of -the formula I prepared according to the invention with the liquid epoxide resin (X~
to obtain pastes which, al-though they show a distinc-t rise in viscosity af-ter storing ~or a period of days, can still be applied as a pas-te even after 90 days and have virtually the same gel time as after storage for 3 days at room temperature.
This is the more surprising because diaminodiphenylmethane, which because of its chemical structure is considerably less reactive, under the same conditions results in a paste which becomes solid after only 3 days storage at room temperatnre.
In accordance with Example I, 34.3 g of 1,4-diamino- ;~
2-p--tolyl~3-phenylbu-tane and 41.2 g of 1,4-diamino-2-(p-chlorophenyl)-3-(p-methoxyphenyl)-butane are each homogenised, by means of a triple roll mill, with 100 g of the same epoxide resin based on bisphenol A, a viscous suspension being obtained.
The characteristics of the mouldings and B-stage resins pre-pared therefrom are given in Table 6 and 7.
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Since they have a lower degree of conversi.on, the solid and fusible B-s-tage resins ob-tained from the amines pre-pared according -to the inven-tion and the liquid epoxide resin based on blsphenol A can be applied more easily than the B-stage resins ob-tained from diaminodiphenylmethane and the same epoxide resin under -the same condi-tions.
materials for the process according to the invention can also be prepared correspondingly. More precise information on the reac-tion is -to be ~ound in the publication by R.B. Davis in J. Amer. Chem. Soc. 80 (1958) 1,752. All of the di-nitriles lis-ted in Table I in this publica-tion can be employed as s-tarting ma-terials ~or the process according to the inven-tion. Other dini-triles not mentioned in Table I can, of course, also be employed if they correspond to the formula II.
The temperature suitable for the hydrogenation accord-ing to stage a) is in each case dependent on -the hydrogena-tion catalyst used. If Raney nickel or Raney cobalt is used, the reaction condi-tions are op-timum, in respect of the yield, when tempera-tures of about 90 to 1~0C are used. When known noble metal catalysts, such as platinum, palladium, rhodium or ruthenium, are employed, the reaction can be carried out at lower temperatures, such as, say, at room temperature.
The hydrogenation can be carried out by the methods customary in the laboratory and in industry, either under normal pressure, for example in a duck-shaped shaking vessel, or under pressure in an autoclave.
Additional inert organic solvents which can be used for the hydrogenation are, for example, hydrocarbons or ethers, such as hexane and dioxane, or aroma-tic compounds, such as toluene or benzene.
The catalytic ~eduction is as a rule carried out by mixing a solution of the particular succinic acid dinitrile of the formula II in acetic anhydride and, if desired, a solvent ~..,;
with the ca-talyst and passing hydrogen gas into the reaction mix-ture. The hydrogenation is continued ~mtil no further hydrogen is absorbed. The catalyst is then separated off.
In -the second stage b), the resul-ting subs-tituted N,N' diacetyl-1,4-diaminobutane is generally firs-t isolated and then subjected to acid or alkaline hydrolysis. In principle~ however, -the hydrolysis can also be carried out withou-t separating OI'f the diace-tyl compound, i.e. direct in the solution, which has been freed from the catalyst, and is ob-tained from stagea)~ The intermediate is isolated by known pro-cesses.
The acyla-ting hydrogenation in -the presence of acetic anhydride employed in stage a) of the process according to the invention is known per se but in the present case ultimately ~ -results in solid, substituted 1,4-diaminobutanes which, sur- --prisingly, are outs-tandingly sultable as curing agents ~or epoxide resins in respect of po-t life, colour s-tability and stability to aggressive media, especially organic acids and alcohols, and some of which are even superior to some con-~entional curing agents. This is the case, in particular, for adduct curing agents obtained from the substituted 1,4-diaminobu-tanes,which can be prepared by the process according to the invention,and liquid polyepoxide compounds.
The 1,4-diaminobutanes of the ~ormula I which can be prepared according to the invention are also particularly suitable for the production of pre-reaction products with epoxide resins (B-stages). For the preparation o~ such - 6 ~
, 3~3L
R-stages, as is known, the corresponding epoxide resin is mixed with the curing agent and the mixture is stored either at room temperature for about 1 to 14 days or at slightly elevated temperature (not higher than 60C) for one or se~eral hours. The B-stages which form during'this storage are : .
u~ed, a~ nown, lnter alia ~ compre3~isn mouldlng compo-sitions, pre-pregs for laminates, sintering powders a~d adhesives. Those based on the 1,4-diaminobutanes of the formula I which can be prepared according to the invention are suprisingly superior to the conventional B~stages which, as is known, contain predominantly aro~atic amines as the ouring agents. This superiority is particularly surprising because the basic character of the 1,4-diaminobutanes o~ the formula I is rather that of aliphatic amines. However, as is known, aliphatic amines are unsuitable in practice for the preparation of B-stages~
The invention further also re:Lates to cura~le mlxtures containing a 1,4-diaminobutane o~ the formula I and a poly-epoxide compound (designated X here) having, on a~erage, more than one epoxide group in the molecule, there being9 in the mixtures, 0.5 to 1.5 equivalents o~ active hydrogen atoms, bonded to nitrogen,.in the particular 1,4-diaminobutane per 1 equivalent of epoxide groups in the epoxide compound (X).
A preferred form of the curable mixtures accordi~g to the invention comprises those which contain the 1,4-diamino-butane of the formula I in the form of an adduct curing agent (E) having an amine number of 4.0 to 4.7 ob-tained from the ~ diaminobutane of the formula I and a liquid epoxide com-pound (designa-ted Z here) having, on average, more -than one epoxide group in the molecule and, if desired, phenylglycide.
In such mixtures there are 0.8 -to 1.2 e~uivalents of active hydrogen atoms bonded to the nitrogen atoms ol the adduct curing agen-t (E) per l equivalent of epoxide groups in the epoxide compound (X). Bisphenol A epoxide resins or bis-phenol F epoxide resins are preferably employed as liquid epoxide compounds (Z) for the preparation of the adduct curing agen-ts (E). The preparation of the adduct curing agents (~) is preferably effected by warrning a mixture of a 1,4-diaminobutane of the forrnula I, an epoxide compound (Z) and, if desired, phenylglycide (molar ra-tio: l.0 : 0.13 : 0.2) to temperatures of 12GC to 200C.
The adduct curing agent (E) can additionally also con-tain 5 to 10% by weight, relative -to the pure adduct curing agent, of salicylic acid as a reaction accelerator.
The invention further also relates to the B-stages which are stable on storage and have already been described and which are to be regarded as a preferred form of -the curable mixtures according -to the invention.
Polyepoxide compounds (X) which can be used for the curable mixtures according to the invention are~ in particular, those having on average more than one glycidyl group, ~-methyl-' ' ', .
315~ :
glycidyl group or 2,3-epoxycyclopentyl group bonded to a -:
hetero-atom (for example sulphur and preferably oxygen or nitrogen~; preferred compounds are bis-(2,3~epoxycyclo-pen-tyl) e-ther; di- or poly-glycidyl ethers of polyhydric aliphatic alcohols, such as 1,4-butanediol, or polyalkylene glycols~ such as polypropylene glycols; di- or poly-glycidyl -ethers of cycloaliphatic polyols, such as 2,2-bis-(4-hydroxy-cyclohexy].)-propane; di- or poly-glycidyl e-thers of poly-hydric phenols, such as resorcinol, bis-(p-hydroxyphenyl)-methane, 2,2-bis-(p-hydroxyphenyl)-propane (= di~methane), 2,2~bis-(4~-hydroxy-3~,5 t -dibromophenyl)-propane, 1,1,2,2-tetrakis-(p-hydro~yphenyl)-ethane or of condensation products of phenols with formaldehyde obtained under acid conditions, such as phenol novolacs and cresol novolacs; di- or poly- -~
(~-methylglycidyl) ethers of the abovementioned polyhydric alcohols or polyhydric phenols; polyglycidyl esters o~ poly-basic carboxylic acids, such as phthalie acid, tereph-thalic acid~ ~4-tetrahydrophthalic acid and he~ahydrophthalic acid;
N-glycidyl derivatives o~ amines, amides and heteroeyeIie nitrogen bases, such as N,N-diglycidyl-aniline, N,N-diglycidyl-toluidine and N,N,N',N~-tetraglyeidyl-bis-(p-aminophenyl)-methane; triglycidyl isocyanùrate; N,N'-diglycidylethylene-urea; N,N'-diglycidyl-5,5~dimethyl-hydantoin and N,N'-di-glycidyl-5-isopropyl-hydantoin; and N,N'-diglycidyl-5,5-dimethyl-6-isopropyl-5,6-dihydro-uracil.
I~ desired, active diluents, for example styrene oxide, ; butyl glyeidyl ether, isooctyl glycidyl ether, phenyl glyeidyl : - ~ ' , ', ';, ~2~
ether~ cresyl glycidyl ether or glycidyl esters of synthetic, highly branched, mainly -tertiary aliphatic monocarboxylic acids ("CARDUR~ E"), can be added to the polyepoxides in order to lower the viscosity.
The curing of the curable mixtures according to the invention -to give mouldings and the like is carried out in the temperature range of 20 to 160C when the free 1,4-diamino-butanes of the formula I are used. However, if the mix---tures contain the described adduct curing agents of -the 1,4- -diaminobutanes, curing is preferably carried out at tempera-tures of 5 to 250C.
In order to shorten the gelling times or curing -times, known accelerators for the amine curing reaction, for example monophenols or polyphenols, such as phenol or dlomethane, salicylic acid, tertiary amines or salts of thiocyanic acid, such as NH4SCN, can be added.
Furthermore, conventional modifiers, such as ex-tenders, fillers and reinforcing agents, pigments 9 dyes, organic sol-vents, plasticisers, flow control agents, agents for conferring thixotropy, ~lameproofing agents and mould release agents, can be added to the curable mix-tures, according to the invention, of polyepoxide compounds (X) and 1,4-diaminobu-tanes of the formula (I) or corresponding adduct curing agents in any stage before curing.
The following may be mentioned as examples of extenders, reinforcing agents, fillers and pigments which can be employed in the curable mixtures according to the invention: coal tar, _j :.. , ~ . .
., .
351 :`
bi-tumen, liquid coumarone-indene resins, -textile fibres, glass fibres, asbes-tos fibres, boron ~ibres, carbon fibres, cellu-lose, polyethylene powders and polypropylene powders; quartz powder; mineral silicates, such as mica, asbestos powder or slate powder; kaolin, aluminium oxide trihydrate, chalk powder, gypsum, antimony trioxide, bentones, silica aerogel ~"AEROSIL"), lithopones 9 baryte, -titanium dioxide, carbon black, graphite, oxide colours, such as iron oxide, or metal powders, such as aluminium powder or iron powder.
Suitable organic solvents for modifying the curable mixtures are, for example, toluene, xylene, n-propanol, butyl acetate, acetone, methyl ethyl ketone, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether.
Examples o~ plasticisers which can be employed for ~-modi~ying -the curable mixtures are dibutyl phthalate, dioctyl ;-phthalate and dinonyl phthalate, tricresyl phosphate, trixyl-enyl phosphate, diphenoxyethylformal and polypropylene glycols.
These plasticisers can also already be constituents o~ the curing agent, especially of the adduct curing agent. In such cases, the plasticisers are present in a concentration of 25 to 50/O by weight, relative`to the pure curing agent.
Examples of ~low control agents whioh can be added when the curable mixtures are employed particu]arly in surface protection are silicones, liquid acrylic resins, cellulose acetobutyrate, polyvinylbutyral, waxes, stearates and the like (some of which are also used as mould release agen-ts).
3~
Particularly for use in the lacquer field, the poly-epoxide compounds can furthermore be partially esterified in a known manner with carboxylic acids, such as, in particular~
hlgher unsa~urated fat-ty acids. It is also possible -to add o-ther curable synthetic resins, for example phenoplasts or aminoplasts, to such lacquer resin formulations.
The curable mixtures according to the invention can be produced in a conventional manner with the aid of known mixing equipment (stirrers, kneaders, rolls, or, in the case of solid powders, mills or dry mixers).
The curable epoxide resin mixtures according to the invention are employed in particular in the flelds of surface protection, -the electrical industry, laminating processes and adhesives technology and in -the building trade. They can be used in a formulation suited ln each case to the particular application, in the unfilled or filled state, if appropriate in the form of solutions or emulsions, as paints, lacquers and solvent-free coatings, as sintering powders, compression moulding compositions~ injection moulding formulations, dipping resins, casting resins, impregna-ting resins, binders and adhe-sives and as tool resins, laminating resins, sealing and filling compositions, floor covering compositions and binders for mineral aggregates.
Example 1 Precursor: N,N'-Diacetyl-1,4-diamino-2,3 diphenylbutane 34.9 g (0.15 mol) of 2,3-diphenyl-succinic acid , ~
. ''' 3~.
dinitri:Le are hydrogena-te~ at 120-125C and under a pressure of 120 atmospheres gauge in 200 ml of toluene and 35.3 g (0.36 mol) o~ acetic anhydride in an autoclave in the pre-sence of 3.5 g of Raney nickel. me absorption of H2 has ceased after 30 minutes and N,N'-diace-tyl-1,4-diamino-2,3-phenylbutane crys-tallises ou-t on cooling. The super-natant solution is decanted off and the residue is boiled wi-th 300 ml of ethanol~ whereupon the produc-t dissolves.
In order to separate of~ the catalyst, the mixture is fil-tered ho-t and the filtrate is partially concentrated. The product then crystallises ou-t and is filtered off a-t room temperature, washed with ethanol and dried a-t 80C. Yield:
30,5 g; melting point: 221-222C. A further 3.4 g of substance are obtained by concentrating, so tha-t the total yield is 33.9 g (69.5% of -theory). For analysis, 1 g is recrystallised from 10 ml of ethanol. Yield: 0.8 g;
melting point 221-222C.
Analysis C20H24N2o2 (molecular weight = 324.41) - calculated C 74.04 H 7.46 N 8.64 ~- found C 74.11 H 7.58 N 8.68 The NMR spectrum agrees with the structure.
1, 4-Diamino~,3~ph~1butanè
385.7 g (1.19 mols~ of N,N'-diacetyl-2,3-diphenyl-1,4-diaminobutane in 715 ml of 5N sodium hydroxide solution are heated to 200C in an autoclave for 16 hours. After cooling, the mixture is extracted with 1,800 ml of chloroform.
Further extraction with 2 times 200 ml of chloroform and concentration of the extrac-ts gives 285.4 g of crude product, which is recrystallised from 2.6 1 of benzene. Yield:
258.5 g of 1,4~diamino-2,3-diphenylbu-tane; melting point:
144-145C. A fur-ther 15.1 g of substance having a melting point of 144-145C are obtained by concentrating the mother liquor; -the total yield is thus 273.6 g (95.7% of ~theory).
For analysis, 1.0 g is recrystallised from 10 ml of benzene.
Yield: 0.88 g; melting poin-t: 144~145C; meso ~orm.
Analysis Cl~H20N2 (molecular weight = 240.34) calculated C 79.95 H 8.39 N 11.66 found C 79.88 I-I 8.31 N 11.69 The NMR spectrum agrees with the structure.
Example 2 Precursor: N,N' Diacetyl 1,4-diamino-2-(p-chlorophenyl)-3-(p-methoxyphenyl)_butane.
29.6 g (0.10 mol) of Z-(p-chlorophenyl)-3-(p-methoxy-phenyl)-succinic acid dinitrile are hydrogenated for 4 hours at 110C and under a pressure of 100 atmospheres gauge in 200 ml of toluene and 25 g (0.24 mol) of acetic anhydride in an autoclave in the presence of 3 g of Raney nickel. The -totàr-reaotion mixture is then concentrated in a rotary evapo-rator, the residue is boiled ùp with 700 ml of ethanol and the Raney nickel is filtered off. After concentrating the fil-trate to 200 ml, the product crys-tallises out. After filtering off, washing and drying, 19.0 g (48.8% of theory) of a substance having a melting point of 235-238C are obtained.
The filtrate is completely evaporated in a rotary e~aporator;
~Z3~
recrystallisa-tion of the residue ~rom 100 ml of ethanol gives a fur-ther 2.3 g of produc-t having a melting poin-t of 232-236C.
To-tal yield: Z1.3 g (54.7% of theory).
1?4-Diamino 2~ chl~x~hen~])-3-~p-methoxy~henyl)-butane , .
21.14 g (0.054 mol) of N,N'-diacetyl-1,4-diamino-2-(p-chloroFhenyl)-3-(p-methoxyphenyl)-bu-tane in 80 ml of 15%
s-treng-th aqueous sodium hydroxide solution are heated to 200C
in an autoclave for 12 hours. Af-ter cooling, the mixture is extrac-ted with chloroform and the organic phase is washed with water and then evaporated in a rotary evaporator.
Yield of crude product: 13.2 g (79.6% of theory) of a crystalline product. For purification, this product is recrystallised ~rom 200 ml o~ cyclohexane, then filtered of~, washed with cvclohexane and dried in vacuo at 60C. Yield:
~,, 11.55 g (69.6% of theory~; melting point: 124-127C.
Analysis C17H21N20Cl (mQlecular weight = 304.82) calculated C 66.99 H 6~94 N 9.19 found C 67.06 H 6.87 N 9.09 ~ ' .
Precursor: N,N'-Diacetyl-1,4 diamino-2-p-tolyl-3-phenyl butane.
24.6 g (0.10 mol) of 2-p-tolyl-3-phenyl-succinic acid dinitrile are hydrogena-ted at`l20C and under 100 atmospheres gauge in 250 ml of toluene and 31 g (0.30 mol) of acetic anhydride in an autoclave in the presence of 2.5 g of Raney nickel until a constant pressure is reached. The total mixture is concentra-ted to about 100 ml in a rotary evaporator, 600 ml of ethanol are added, the mixture is heated to the - 15 ~
2;3S3L
reflux temperature and the ca-talys-t is filtered off hot.
Af-ter concen-trating the flltra-te to about 300 ml, -the product crystallises out on cooling in a refrigerator. Yield:
18.5 g (54~6% of theory); melting po~nt: 226-7C. A
fur-ther 3.0 g (8.9% of theory) of produc-t having a melting point of 222-6C are ob-tained by concen-tra-ting the mother liquor. Recrystallisation of 0.80 g of the ~irst frac-tion from 12 ml of e-thanol gives 0.49 g of pure product having a melting point of 226-7C.
~nalysis C21H26N202 (molecular weight = 338.45) calculated C 74.53 H 7074 N 8.28 found C 74.39 H 7-71 N 8.49.
~ i! 18.6 g of N,N~-diacetyl-1,4-diamino-2-p-tolyl-3-phenyl-butane in 80 ml of 15% strength aqùeous sodium hydroxide solu-tion-are heated to 200C in an au-toclave for 16 hours~ On concentrating the solution, the amine partially crystallises out. The mixture is extracted 3 times with 50 ml of chloroform and after evaporating the extracts in a rotary evaporator 13.8 g of crystalline crude amine are obtained.
Recrystallisation from 110 ml of cyclohexane gives 12.2 g (87.3% of theory) of diamine having a melting point of 112-14C.
Analysis C17H22N2 (molecular weight = 254.38 calculated C 80.27 H 8.72 N 11.01 found C 80.05 H8.64 N 11.34.
. ~ , .
, ~ .
, ' ' ,~ ' . .
,:,.. , ~ .
3~l .
Precursor: N,N'-Diacetyl-1,4-diamino~2-(p-dimethylamino-phenyl)-2-phenyl butane.
13~4 g of 2-(p-dimethylamino-phenyl)-3-phenyl-succinic acid dinitrile are hydrogena-ted a-t 120C and under 100 atmos-pheres gauge in 250 ml of toluene and 15 g of acetic anhydride in an autoclave in the presence of 1.5 g of Raney nickel until constant pressure is reached. The mixture is concentrated to 50 ml, 300 ml of e-thanol are added and J a~ter boiling up, the catalyst is filtered off. All of the solven-ts are then removed in a rotary evaporator and the reside is recry-stallised from 60 ml of acetonitrile. 3.1 g of a product having a melting point of 205-9C are obtained in the first fraction. The NMR spectrum is in agreement with the ~`
structural formula ~ ~ ~ ' 19.1 g of N,N'-diacetyl-1,4-diamino-2-(p-dimethyl aminophenyl)-3-phenyl-butane in 80 ml of 15~ strength aqueous sodi~n hydroxide solution are heated to 200C in an autoclave for 16 hours. The reac-tion solu-tion is then concentrated in a rotary evaporator and extracted with chloroform. After . .
removing the chloroform in vac~o, 8.5 g of crys-talline crude amine are obtained and this is recr-ystallised from 35 ml of isopropanol. Yield: 3.8 g of product having a melting point o~ 145-146C. A further 2.0 g of product having a melting point of 145-146C are obtained by concentrating.
Analysis C18H25N3 ~molecular weight = 283.
;
s~
calculated C 76.28 H 8.90 N 14.8~
found C 76.26 H 8.93 N 14.74.
B) Use Ex~
-(Casting and adhesive resin) 31.8 g of 1,4-diamino-2,3-diphenylbutane are homogen-ised, by means of a triple roll mill, together with ~00 g of a liquid unmodified epoxide resin (X) which is based on bis phenol A and has an epoxide content o~ 5.3 equivalentjkg and a viscosi-ty of 10 9 800 cP/25, a viscous white suspension being obtained.
The following methods are used to determine the various characteristics:
Differential thermal analysis is used to determine -the reactivity. About 20 mg of -the resin/curing agent mixture to be tes-ted are warmed in a small Al crucible in the measuring chamber of a type TA 2000 differential thermoanalyser from Messrs. Mettler (Greifensee, Switzerland) at a heating rate of 4/minute and the temperature difference between this crucible and an empty crucible warmed at the same time is recorded continuously. The temperatures for the start of reaction, for the maximum reaction rate and for the end of the reaction are read off, as parameters characterising the reactivity, ~rom the curve thus obtained. The area under the`curve enables the heat liberated during the reaction to be determined and gives an indication of the completeness of the conversion.
..
~, , :;` ' ~
b) Determination of_-the lass transition -temperature '4 g of -the resin/curing agent mix-ture are, in each case, poured in-to a thin-walled Al crucible of about 5 cm diame-ter and cornpletely cured in this crucible (4 hours at 80C and 8 hours at 140C). A sample is -taken from the disc thus obtained in order to determine the glass transition temperature of -the crosslinked polymer with the aid of differ-en-tial thermal analysis. The specific heat changes at the transition point; this change is registered as a turn-ing point in the curve recorded by the DTA apparatus.
Conclusions regarding the dimensional stabili-ty of the result~
ing polymer when ho-t can be drawn from the glass transition tempera-ture.
c) Determination of the mechanical and dielec-tric properties The resin/curing agent mixture prepared as described above is poured into aluminium moulds, which have been pre-treated with mould release agents, in order to produce sheets having dimensions of 135 x 135 x 4 mm and 135 x 1~5 x 2 mm and the sheets are cured for 4 hours at 80C and 8 hours at 140C.
The 4 mm thick sheets~are used to produce test pieces having dimensions of 60 x 10 x 4 mm for determining the flexu-ral strength and deflection according to VSM Standard Specifica-tion 77,103, the impact strength according to VSM
Standard Specification 77~105 and the increase in weight after storage in water.
'' ,, . .. , : ~
~235~L
The 2 mm thick sheets are used to determine the diélectric properties.
d~_Test to deter ne the suitabil ty as an adhesive A small amoun-t of the resin/curing agent mixture is applied, in each case, -to the ends of test strips made of anticorodal B which have dimensions of ]70 x 25 x 1.5 mm and have previously been roughened by grinding and degreased by washing with solven-ts. In each case, two of these test strips are so adjusted with -the aid of a gauge that the ends coated wi-th resin/curing agent mixture overlap by 12 mrn.
After fixlng with a clamp, the adhesive is cured and after cooling the clamp is removed and the -tensile shear strength o~ the glue bond is then tested in a tensile test (DIN 53,183~.
~ ::
A small amount of the resin/curing agent suspension is distributed on a sheet of glass by means of a glass rod so that a uniform film is obtained. The coating obtained after curing is tested to determine its chemical stability by leaving a drop o~ the par-ticular chemicals on the film ~or 1 hour. The chemicals are then wiped off and the sur~ace of the film is assessed visually.
The characteristics de*ermined for the various test ?
pieces by the methods mentioned are summarised in Table 1.
EXample I shows -that mixtures of 1,4-diamino-2,3-diphenylbutane and epoxide resins are very reactive and give mouldings with good mechanical and electrical proper-ties and a high glass transition temperature. If the mix-tures are .
'' ~ .
~Z.~
applied in a thin layer in the form of a solven-t-free coa-ting, films are obtained which have very good stability towards solven-ts and aggressive chemicals in aqueous solution.
Mixtures of thls type can also readily be used for glue bonds.
Table 1 (relating to Example I) 100 par-ts of epoxide resin Sys-tem based on bisphenol A
31.8 parts of 1,4-diamino-2,3-diphenylbutane ~ , T~ 2000 TRRmax 102 En-thalpy 20,815 cal/equivalent of epoxide/amine sys-tern Curing 4 hours at 80C
Appearance of -the moulding material whlte, opaque ~ . _ Impact strength (cmkg/cm2) 5-5 Flexural strength (kg/mm2) 9.2 Deflection (mm) 3.2 Glass -transition temperature (C) 151 Absorption o~ H O, 4 days at room tempera-ture2 ~%) 0.29 Absorption of H20, 1 hour in boiling water (%) 0.63 Tensile shear streng-th (kg/mm2~ 1.7 _ Chemical stabili-ty towards .
5N NaOH no attack o~ any type .H20 . de-tectable acetone -Cl-benzene Loss fac-tor tan ~
>1% above 79 ~5% above 104 Dielectric constant at 25C 3.6 Specific volume resistivity 25 (~xcm) 4.7x1016 , LL~
TRRmaX = Temperature a-t the maximum ra-te of reaction TS = Temperature a-t -the star-t of the reaction TE = Tempera-ture a-t the end of the reaction (Solvent-free coating systems) Preparation of the_adduct curin~ a ents Addwct curin~ agent I according -to the invention 50 g of a liquid epoxide resin (Z) based on bisphenol A and having an epoxide equivalent weight of 168 and a vis-cosity of about 37400 cP (25C) are mixed together with 180 g o~ diphenoxyethylformal and 240 g of 1,4-diamino-2,3-diphenyl-butane in a -three-necked flask and the mixture is heated to 150C. 30 g of phenylglycide are then added dropwise and the mixture is reacted at 150-170C for 25 minutes. After cooling to about 120C, 35 g of salicylic acid are melted into the mixture, with stirring. The finished adduct curing agen-t is-discharged at about 50C. Charaoteristics: see Table 20 (as comparison) Base~ on: 4,4' diamino-diphenylmethane.
Table_2 (Charac-teristics of the curing agents according to Example II) . . .. . ~ _~ ~
Curing Viscosi-ty Amine H equivalen-t Suitable mixing agent a-t 25C in number weight ra-tio of epoxide cP (accord- resin to be cured:
ing to adduct curing Ho0ppler) agent . .. ._ ~ ~_... ~ - . .. . . . .~
I ~100,000 4.5 127 100:66 _ _~ _ __ . .
II 6,700 4.5 115 100-60 ~ 23 -,_,, .. , .. . , .,.. ,.. ,,.. , ., ., .... ... ............ , ... ........ ,... , . ... .. ... , -.-P~
A liquid bisphenol A epoxide resin (X) hav:ing a vis- :
cosi-ty of 11~300 cP at 25C and an epoxide equivalent weigh-t of 194 is mixed wi-th -the aclduct curing agent I in a weight ratio of 100:66 (mix-ture I). An analogous mixture is also prepared using the conventional adduct curing agent II (mix-ture II). In both cases, cleaned, 0,8 mm thick steel sheets are coated -to a thickness of 200 ~m (thickness of the wet film) wi-th the mix-tures I and II. These metal sheets are used to de-termine -the properties in respect of lacquer technology and these properties are compared in Table 3. In :
order -to test the stability towards dilute acetic.acid and ::
alcohol, fur-ther steel shèets are coated -to a layer thickness of 300 ~m. The corresponding results are compared in Table L~, ' .
- 24 - ~ -'I ' ~ , ' ' ' ' '" " ' ,;
.
, p~s~
(Proper-ties in respect of lacquer -technology for mixtures I
and II and -the coatings produced) _ Mixture I II
. . . _ , . . , , , _ _ Gel time for 100 ml (Tecam appara-tus) >210 mins. 140 mins.
Viscosity of the mixture (25C) cP ~ 50,000 9,000 Time for drying to -touch¦hours 7 12 Through-curing -time/hours 20 15 Appearance of the film 20/65%
relative humidity good good Appearance of the film 20/100%
relative humidity good good Appearance o~ -the film 5/45%
relati~e humidity . good good Hardness (Persoz) seconds/7 days 320 345 Erichsen ~l/m/7 days 3 - 5 C 2 Impact cmkg 30-40 ~ 40 Adhesion on sand-blasted sheet steel good moderate Stabili-ty to boiling water (6 hours/96C) good good ~ 72 rJ 72 Table 4 __ (Stabili-ty of -the coatings towards dilute acetic acid and ethyl alcohol in months Layer thickness: about 300 ~m on sand-blasted sheet steel, curing 10 days) . _ , _ ~ ~ , _, ~
Mixture I II III IV
_~ ~ __ , _ _ , Acetic acid, 5%~6 ~12 ~12 1 D
. Acetic acid, 10% ~6 ~12 ~ ~ 1 D
Ethanol, 20% ~ ~12 ~7 Ethanol, 50~0 1-6 A 7-9 D C 1 D _ -- . . , , ,~ , ~. ,,."~ __ _ ~ ~
;3S~IL
Legend: 1-6 A signifies: Film a-ttacked, for example softer or formation of bubbles 9 from 1~6 months 1 ~ signi~ies: Film destroyed before 1 month ~6 and ~8 signifies: Film intact after 6 and 8 months respec-tively (test con-tinued) Mixture III containing~ curing agent III = adduct (associate) of 4,4'-diamino-3,3-dimethyl-dicyclohexylmethane and nonylphenol Mixture IV containing: curing agent IV = adduct (associate) of trime-thylhexamethy-lenediamine and nonylphenol.
r~AI~t~~ ~ tb~ l~s~lt~ ~
If the processing charaoteristics, which are very important industrially, and the properties in respect of lacquer technology which are achieved with the coatings are first compared with the aid of Table 3, the curable mlx-ture I
containing the adduct curing agent I based on 1,4-diamino-2,3-diphenylbu-tane has a longer po-t life (of ~210 ~inutes) com-pared with the mixture II containing the adduc-t curing agent II based on 4,4l-diamino-diphènylmethane and this ~acilitates easy processing by hand with a brush and roller, for which there is a great demand in practice.
Some of the other properties in respec-t of lacquer -~
tec~mology of such coatings are superior to the properties of coatings which contain curi.ng agents based on conventional '~.
_ 26 --.. . . . . . . .
.. . . .
~"': ;' ,' : , , : :
S~
aromatic amines. The colour stability of the novel aclduct curing agent I is significantly be-tter and -this rnakes it possible, for example, to produce whi-te-pigmented coatings.
In respec-t of the stabili-ty to highly aggressive media such as dilute organic acids (5/0 st,rength and 10% strength ace-tic acid) and also 20% and 50% ethyl alcohol, which are a factor de-termining -the quality in the foods-tuffs sec-tor, -the novel adduc-t curing agent I shows up very well when compared with the curing agent based on 4,4'-diaminodiphenylmethane and is distinc-tly superior to the other conventional curing agents based on aliphatic and cycloaliphatic polyamines (compar-ison mixtures III and IV, Table 4).
Example III
(Pre-reaction product which is stable on storage; B-stage) The resin/curing agent mixture described in Example I
and a suspension prepared from 100 parts by weight of -the same epoxide resin ~X) and 26.2 parts by weight of 4,4'-diamino-diphenylmethane, which is intended to enable a comparison to be made with the state of -the art, are stored at room temp-erature (RT) and their reactivity and their softenlng range are checked at specific intervals. Two different experi-mental methods are used for this purpose:
a) Determination of the gel time at 120C on a thermo-statically controlled hot-pla-te and b) Determlnation of the reactivity using the ~ifferential Thermoanalyser already described above.
In addition to changes in the temperatures for the , . .
L
melting point, the star-t of reac-tion and -the reac-tion maximum 7 the de-terminati.on of the hea-t of reaction fur-ther liberated during complete curing of -the pre-reaction products in parti-cular enables an assessment to be made of the degree of conversion be~ore and after s-torage of the pre-reac-tion produc-t.
The values determined ~or the two systems by the methods mentioned are summarised in Tablë 5.
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_ O _ a~ ~ r~O ~ O
_ _ ~D _ , ~ C~ r~
l ~D _ ~
~ _ _ _ r~ ~ 0 ~O O a:
r~ C~ ~1 a~ ~ .
_ _ ;~ _ w u~
~0~ _ r~ r-l 0 h _ _ _ ri ~ 0 ~
_ _ . ._ ~ ,1 _ ~ ~ ~ ~
rO ~3 ~ CD I rl ~ O
~ ~ a~ ~ .~ . o ) 115 h _ r~ ~ ~ O ~ hl ~ 'OR ~ _ C~l h O
_ _ _ _ _ . C) q) _ ~ ~0 ~ O ~O ~ ~ 0 0~ O h~ h~"~l r-l ~\ ~ ~ hl ~, . > ,~ ~ rt h ~¦
~ U~ O = ~t ~ h--\ 8 ~ ~ x ¦
~1 P~ ~ U~ rl~ ~ r~ ~ 5~
~ _ ~ ____ ~ ~
;~ _ ~O ~ O h'~ 8 h~ ~
~'I 1~ h ,~ O ~ h~ a~ ~D
~ ~ ~ 4 h r~ h ;f / ~ r~ O ~ h h X _ _ ~O ~ O O , C~ I<'`\ ~I rl O ~ ~ ~ ' ~ ~ _ _ . r1 ~ ~1 .
~$ ~ o o . ~ . I ~
O _ r~ O ;t ~1 ~ I
. f ~ _ ~ ~ ~
_ _ _ _ _ ~
~ ~ ~o ~ ~ .
~rl Ul ~ .~1 h O.C O ~ ~ ¦
O O ~ O ~ ~' ul O O O ~/ rl WJ
~ bD~ ~ .~ 8 ~ ~ ~ ~ 8 ~ h $ ~
W O ~ rJ O r l ~ 1~ ~ O h~ ~ ~J r+~ ,R ~ 1-l 1:
3 ~ ær~ æ~
_ _ _ .
-- 29 -- .
Evalua-tion of the results _ According to Example III it is surprisingly possible by simply grinding the solid amine of -the formula I prepared according to the invention with the liquid epoxide resin (X~
to obtain pastes which, al-though they show a distinc-t rise in viscosity af-ter storing ~or a period of days, can still be applied as a pas-te even after 90 days and have virtually the same gel time as after storage for 3 days at room temperature.
This is the more surprising because diaminodiphenylmethane, which because of its chemical structure is considerably less reactive, under the same conditions results in a paste which becomes solid after only 3 days storage at room temperatnre.
In accordance with Example I, 34.3 g of 1,4-diamino- ;~
2-p--tolyl~3-phenylbu-tane and 41.2 g of 1,4-diamino-2-(p-chlorophenyl)-3-(p-methoxyphenyl)-butane are each homogenised, by means of a triple roll mill, with 100 g of the same epoxide resin based on bisphenol A, a viscous suspension being obtained.
The characteristics of the mouldings and B-stage resins pre-pared therefrom are given in Table 6 and 7.
, ~ -~--~ o o ~ 'F~ ~ h h ~i I (~ ) ,~
~) p, ~ ,H -l~ O a) h O <:C ~H ~~ ~ ~ u~ ,r~l Pl O
~r~l ~ O J I ~ ~ CO ~) -1~
o r~ ~ ~ ,~ ~l O ~ ~ tl~
Pl O r~ r-l I a) ~:~ h a) a~ ,~r~ ,~ ~ ~H O (J~ a) h I
p,tH ,_~ ~1 r~ 1 O r-l O
t~l U~ O C) ~ ~ 0 ) ~H ,Q ~H
O ,~ ,r~ ~r~ O ~ ~ O ~r~ O ~ O
u~ p~ a) o o o o +~ ~ ~ t) o ,~ ~ o u~ o ~ ~ ~ ~ ,~ ~, a) 0 ~
h h ~ J O (~ O~ r-lo a)~ a~ o h O lT;~ o ~r~ r-l ~D X u~ Or~ ~5 0 ~I h ~d p~(--l X ^ O h O -1~ u~ hl ~) P~ ~ O O ~ ~ ~-r-l tH h O u~ 01 a) o r~ ~1 ~ ~ ~H
O ~) r~ pl a) 1~ O , E3 ~ O
r-l P ~ `~ Ei J ~ ~q '~ 1 0 ~d ~ ,r,~
~ ~ _ __ ~ jql ~11 .
~r~ ~ t~ ~ h t~ ~) 0 h ~1 a) ~ o O a) a) a) (~ ~ ~r~ ,S~ a) h h S-l (I) ~ r~ t~ ,5 rl Q~
'd r~ ~ ~ 0 ~7 -1 H r~ (L~
g 1 ~ ,Q r-l ~) + . ~a) a) a ~ q r~ ~ ~ O' L~ ~ a) ~ ~ ~
~D ~CH a~ o o o X o . r-l a~
tH ~q O ,r~, ~ O ~D O O(X) O r-l tH r E-l E-l E-l¦
(I) O r~ P1 ~1 0 0 1~ ~ 1~ O r-¦
r~ ,O tQ I r~l (~J ~ G) ~ r~ h ll 1} ll ro ~q ~ ~ .~ ~ ,~ ~1 ~ -1~ ,q h I 1_l tl l O O
E-l h 0 ~ r~ ~J O tq O ~ O
td ~ ~ h O +~ ~q ~J
Q~rd ~1 ~ ~ +~
o ~ O O rl ~ 'd ~:;
8-~d~ I 1~ O E~
-l ~0 ~ ;i -- K .~ j _ _ ~_ E I E~ ~1 ah h $~ aq tq~ _~ ~ ~r~ O +~
~rl O V tn r~ ~ a) N
~q ~rl O rl U~ O q q) CH
~3 r~l rl t~ '1~ ~ ~; $ ~O O
a) ~ u~ a~ a~ ~ o a) I h 1~ rl O ~ ~1 ,q tq ~ ~1 O
: ~q 8 h i~ ~q Lr~ Lr\ ~tl~ V r-l u~ ~ ~ ~ ~ ax~î ~ ~q ~d tl~ bO h r-l E O~d ~r~1 El ~ ~ tq a) rl F rl h t~
h ~1 ~1 tq p.~ ~q ~ . ~ ~ r-l a~ ~ ~ El q ~LO a) ~: Q
, __ ~... __ ,~ C~+~ ~ V-l-) ~i 35i~
_ ~ ~.
~1 (~ _ ~ rc~ Cl ) O Lt`\ ~
~ a) 1~ 1~ I--1 rl U~ r~ ~D ~
r-l ~ O ~ ~O
~Q 0-1~ u~ ~
Sa~ SO ~ . . _ . _ g ~1 1 O Ll~ O ~d ~ 0~ L~ ~:) ~1 a~ ~ ~1 ~ t'\l r~ ~ O O
~d c~ ~ ~1 ~I C-- t~l O
~ O ~ ~O ~r ¦ 0 X P~ ~ ~ ~ ~1 O ~ ~ _ _ __ Pl i ~ _ 0 (L~ ~ Ir~ ,--I 1~ rd t\l cr~ l (1~
CL~ O ~ ~\1 ~ LS`\ 0~ 0 ~ F~ O
~ o o ^ ~o a) (l) ~o'~l~ _ _ ___ _ ~, ~ ~ .
~: a) a~ u~ S-ll C) ~rl ~3 bL) _ O ~ 1~ 0 0 i 4--1 ,5~ r~ I 0 Il~ O O ~ O CO O E~
~1 I F4 h ~ r I Or~ Ir~
D~ O _ tq .~ ~) E3 ~ ~ I O -1) ~ .,~ O h ~rl ~u~ ~ C~l ~01 U~l ~
~ a~
_. ...., =~
~r~ ¦ _ a) ~I) U~ 1~ O O ~_ r~ O() J O C~
i 1-l Ll~ ~1 ~ O r~ ~D
u~S ~ r~ r~ r-l~\J ~ .1 a~.~ o ~ 0 ~0a~ ~1 u~ OC) h S~
0r o _ _ _ _ . ~O ~ ~ O 1~ rc~ ~ ~ O ~ a) (L) 1 L~ ~J ~1 L~ 'O O L~`l E-l E-~_a~ C\J r~ r~ ~\1 11 11 ~ ~ ~ 0 u~ ~
Or~ rl ~ _ ~ _ __ X, r-lO ~; ~ w rQjr,~ ~ ~Q (I) U~
t~(I) ~rl r~ ~0 _ O ~; ~ O O I ~
E-l,s~ rCl ~ S01 ~ ~ E-l E~;
1~ a) o ............... u~ ..
~r J r~ ,~ O -1~ 1~~rl r-l a:!, r~ t~ ~ u~ ~ t~l .
. __ __ ._ ~ ~1 ~ _ ~0+, ~
E~ a> ~ o ~ --~ a) ~>
~) ,~ ~r-l O ~ ) r~
o ~) rc~ ~ U~ O O O ~
+> O r~ .r~ .
0 ~ ^ 0,5:~ u~ ~ CH ~H
r-l ~ ~ ~ ~ S~ ~H O
(I) U~ ~rl 1--l ~r ~ .
~3 El ~ r~ 0 ~rl r-l ~
a~ ~rl 0 ~r-l h ~! 0 0 ~ O
~ .~ E; ~3 0 r~ O r-l r/ ~ri Ul ~1l) ~ ~rl ~rl 0 1lO 0 0 ,r, X ~ h 0 0 -1~ +~ 0 ~ O ~r~
h rd ~ h h C~ r-l O r-l r-l r-l a~ O a~ r-l ~ r-l ~ o ,r~ a) a~ 0 ~ -1 ) ~ c~ O ~
U~ ~l ~) , C~ Ei ~ ~:1 ~ 32 ~
3~
Since they have a lower degree of conversi.on, the solid and fusible B-s-tage resins ob-tained from the amines pre-pared according -to the inven-tion and the liquid epoxide resin based on blsphenol A can be applied more easily than the B-stage resins ob-tained from diaminodiphenylmethane and the same epoxide resin under -the same condi-tions.
Claims (9)
1. A process for the preparation of a 1,4-diamino-butane of the formula I
(I) wherein R1 is H or -CH3 and R2 and R3 independently of one another each denote a radical of the formula or , in which A is alkyl having 1 to 3 C atoms, -OCH3, -N(CH3)2, -Cl or -Br, and R2 is also alkyl having 1 to 3 C atoms, wherein first a) a succinic acid dinitrile of the formula II
(II) is catalytically hydrogenated at temperatures of 20° to 150°C in the presence of acetic anhydride and, then b) the N,N'-diacetyl-1,4-diaminobutane obtained by the hydro-genation is subjected to acid or alkaline hydrolysis in an aqueous medium and finally c) the 1,4-diaminobutane of the formula I is isolated either in the form of a salt or, after neutralisation with alkali, in the form of the free base.
(I) wherein R1 is H or -CH3 and R2 and R3 independently of one another each denote a radical of the formula or , in which A is alkyl having 1 to 3 C atoms, -OCH3, -N(CH3)2, -Cl or -Br, and R2 is also alkyl having 1 to 3 C atoms, wherein first a) a succinic acid dinitrile of the formula II
(II) is catalytically hydrogenated at temperatures of 20° to 150°C in the presence of acetic anhydride and, then b) the N,N'-diacetyl-1,4-diaminobutane obtained by the hydro-genation is subjected to acid or alkaline hydrolysis in an aqueous medium and finally c) the 1,4-diaminobutane of the formula I is isolated either in the form of a salt or, after neutralisation with alkali, in the form of the free base.
2. A process according to claim 1, wherein a succinic acid dinitrile of the formula II is used in which R1 is H or -CH3, R2 is one of the radicals , , or alkyl having up to 3 C atoms and R3 is one of the radicals , or it being possible, for R2 and R3 to be identical or differ-ent.
3. A process according to claim 1, wherein a succinic acid dinitrile of the formula II is used in which R1 is H
and R2 and R3 are each a radical of the formula or , in which A is alkyl having 1 to 3 C atoms, -OCH3, -N(CH3)2, -Cl or-Br.
and R2 and R3 are each a radical of the formula or , in which A is alkyl having 1 to 3 C atoms, -OCH3, -N(CH3)2, -Cl or-Br.
4. A process according to claim 1, wherein the succinic acid dinitrile of the formula II which is employed is a succinic acid dinitrile of the formula ,
5. A curable mixture comprising a) a 1,4-diaminobutane of the formula I
(I) in which R1 is H or -CH3 and R2 and R3 independently of one another each denote a radical of the formula or , in which A is alkyl having 1 to 3 C atoms, -OCH3, -N(CH3)2, -Cl or Br, and R2 is also alkyl having 1 to 3 C atoms, and b) a polyepoxide compound (X) having, on average, more than one epoxide group in the molecule, there being, in the mix-ture, 0.5 to 1.5 equivalents of active hydrogen atoms, bonded to nitrogen, in the particular 1,4-diaminobutane per 1 equivalent of epoxide groups in the epoxide compound (X).
(I) in which R1 is H or -CH3 and R2 and R3 independently of one another each denote a radical of the formula or , in which A is alkyl having 1 to 3 C atoms, -OCH3, -N(CH3)2, -Cl or Br, and R2 is also alkyl having 1 to 3 C atoms, and b) a polyepoxide compound (X) having, on average, more than one epoxide group in the molecule, there being, in the mix-ture, 0.5 to 1.5 equivalents of active hydrogen atoms, bonded to nitrogen, in the particular 1,4-diaminobutane per 1 equivalent of epoxide groups in the epoxide compound (X).
6. A mixture according to claim 5 which comprises a 1,4-diaminobutane of the formula I in which R1 is H or -CH3, R2 is one of the radicals , , or alkyl having up to 3 C atoms and R3 is one of the radicals , or it being possible for R2 and R3 to be identical or differ-ent.
7. A mixture according to claim 5 which comprises, as the 1,4-diaminobutane of the formula I, 1,4-diamino-2,3-diphenyl-butane which has a melting point of 144° to 145°C
and is in the meso form.
and is in the meso form.
8. A mixture according to claim 5 which comprises the 1,4-diaminobutane of the formula I in the form of an adduct curing agent (E) having an amine number of 4.0 to 4.7, said adduct being obtained from the 1,4-diaminobutane of the formula I and a liquid epoxide compound (Z) having, on average, more than one epoxide group per molecule, and optionally phenylglycide, there being, in the mixture, 0.8 to 1.2 equivalents of active hydrogen atoms bonded to the nitrogen atoms of the adduct curing agent (E) per 1 equi-valent of epoxide groups in the epoxide compound (X).
9. A mixture according to claim 8 which comprises an adduct curing agent (E) which has been prepared by reacting the 1,4-diaminobutane of the formula I with the epoxide compound (Z) and optionally with phenylglycide, at a tem-perature of 120° to 200°C, the 1,4-diaminobutane, the epoxide compound (Z) and the phenylglycide having been in a molar ratio of 1.0:0.13:0.2 in the reaction mixture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1557276 | 1976-12-10 | ||
| CH15572/76 | 1976-12-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1102351A true CA1102351A (en) | 1981-06-02 |
Family
ID=4410222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA292,713A Expired CA1102351A (en) | 1976-12-10 | 1977-12-08 | Process for the preparation of 1,4-diaminobutane derivatives |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5373547A (en) |
| CA (1) | CA1102351A (en) |
| DE (1) | DE2754509A1 (en) |
| FR (1) | FR2373512A1 (en) |
| GB (1) | GB1545405A (en) |
| SE (1) | SE7714016L (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01202511A (en) * | 1988-02-05 | 1989-08-15 | Nissan Motor Co Ltd | Suspension device |
-
1977
- 1977-12-06 GB GB50691/77A patent/GB1545405A/en not_active Expired
- 1977-12-07 DE DE19772754509 patent/DE2754509A1/en not_active Withdrawn
- 1977-12-08 CA CA292,713A patent/CA1102351A/en not_active Expired
- 1977-12-09 SE SE7714016A patent/SE7714016L/en unknown
- 1977-12-10 JP JP14868477A patent/JPS5373547A/en active Granted
- 1977-12-12 FR FR7737356A patent/FR2373512A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE2754509A1 (en) | 1978-06-15 |
| SE7714016L (en) | 1978-06-11 |
| GB1545405A (en) | 1979-05-10 |
| FR2373512B1 (en) | 1981-08-07 |
| FR2373512A1 (en) | 1978-07-07 |
| JPS6211009B2 (en) | 1987-03-10 |
| JPS5373547A (en) | 1978-06-30 |
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