CA2214625A1 - New polyamines containing ester and amide groups - Google Patents
New polyamines containing ester and amide groups Download PDFInfo
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- CA2214625A1 CA2214625A1 CA 2214625 CA2214625A CA2214625A1 CA 2214625 A1 CA2214625 A1 CA 2214625A1 CA 2214625 CA2214625 CA 2214625 CA 2214625 A CA2214625 A CA 2214625A CA 2214625 A1 CA2214625 A1 CA 2214625A1
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- diamine
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
- C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3253—Polyamines being in latent form
- C08G18/3259—Reaction products of polyamines with inorganic or organic acids or derivatives thereof other than metallic salts
- C08G18/3262—Reaction products of polyamines with inorganic or organic acids or derivatives thereof other than metallic salts with carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Polyamines containing an ester group and an amide group having the following formula:
(see fig.I) (where R and R" are a divalent linear, branched or cyclic hydrocarbon radical of 4 to 18 carbon atoms: R' is an alkyl radical of 1 to 14 carbon atoms, X is NH or NR''', and R''' is an alkyl radical of 1 to 14 carbon atoms) are useful as a component of a two-pack polyurethane adhesive.
(see fig.I) (where R and R" are a divalent linear, branched or cyclic hydrocarbon radical of 4 to 18 carbon atoms: R' is an alkyl radical of 1 to 14 carbon atoms, X is NH or NR''', and R''' is an alkyl radical of 1 to 14 carbon atoms) are useful as a component of a two-pack polyurethane adhesive.
Description
CA 0221462~ 1997-09-0~
Polyamines cont~; n; nq ester and amide qroups The present invention relates to a group of novel polyamine cont~; n; ng an ester group and an amine group, and to a process for their preparation.
The preparation of a reaction product of a diamine and two moles of maleic ester is described in DE-A 16 70 812 as an intermediate stage in the preparation of hydatoins. The use of this aspartic acid derivative (PADE for short) as a reaction component of a polyisocyanate for preparing a coating takes place in EP 0 403 921. In EP 0 470 461, the use of the aspartic acid derivative PADE (+ polyisocyanates) is claimed as a two-component binder combination in an automative refinish. Surprisingly, the literature contains no reference to the use of the aspartic acid derivative for preparing a two-component (two pack) polyurethane (PU) adhesive. As our own experiments show, bonds produced using the PADE and a polyisocyanate exhibit only moderate tensile shear strength.
It has surprisingly been found to be possible to bring about a considerable increase in the tensile shear strength if the aspartic acid derivative employed for bo~; ng contains at least one amide group.
The present invention accordingly provides a polyamine cont~;n;ng an ester group and an amide group, of the formula:
CA 0221462~ 1997-09-0~
R 1~ R R
R'O--C--CH2~ ,CH2--C--X--R"--X--C--CH2' ,CH2--C--OR' CH--N--R--N--CH~ ,CH--N--R--N--CH~
R O fi H H- fi fi H~ H fi--OR' o O O O
where the substituents are defined as follows:
R and R" are each a divalent linear, branched or cyclic hydrocarbon radical of 4 to 18 carbon atoms, wherein the cyclic hydrocarbon radicals may be substituted with one or more C1-C4 alkyl groups, R' is an alkyl radical of 1 to 14 carbon atoms, X is NH or NR"', and R''' is an alkyl radical of 1 to 14 carbon atoms, wherein R, R' and R" may each have one or more oxygen atoms in place of a CH2 group.
The novel compound preferably has a basic amine content of from 1.5 to 4 mmol of NH2/g, an ester group content of from 3 to 7 mmol/g, more preferably from 4 to 6.5 mmol/g, an amide group content of from 0.6 to 2 mmol/g, more preferably from 0.8 to 1.7 mmol/g, and an NH functionality of from 2.5 to 4, more preferably 3. They may likewise be in admixture with up to 3 moles of compounds of the formula A
described hereinunder.
The viscosity of the novel compound at 23~C varies within a wide range, for example, from 1000 to 10 mPa.s.
The novel compound can be processed without problems, either in solvent-free form or in an inert solvent, with a polyisocyanate to form a two-pack polyurethane (PU) CA 0221462~ 1997-09-0~
coating material. A preferred field of application of the novel compound is the use as a reaction component for the preparation of two-pack polyurethane (PU) adhesive.
The present invention additionally provides a process for preparing the novel compound, which comprises reacting a product of the reaction of a diprimary diamine and maleic or fumaric ester (molar ratio 1:2) of the following formula:
1~l 1~l R'O--C--CH2, ,CH2--C--OR' CH--N--R--N--CH (A) R'O--IC H H 'C--OR' wherein R and R' are as defined above, with a diamine HX-R"-XH
contA;n;ng two primary or one primary and one secondary, or two secondary amino groups. The reaction may be carried out in such a way that from about 2 to 5 mols of the compound (A) is used per mole of the diamine.
The starting compound (A) employed in the novel process is known and is described in EP O 403 921.
The starting compound (A) employed in the novel process may be prepared in a m~nner known per se by reacting a diprimary diamine H2N-R-NH2 with 2 mol~ of maleic or fumaric ester as illustrated by the following scheme:
CA 0221462~ 1997-09-0~
Il O O
H2N--R--NH2 + 2 HC 'OR' ~ ,CH--N--R--N--CH 2 HC'C'OR R'O--ICl H H ICl--OR' o O O
(A) Examples of the diprimary diamine which may be used for preparing the compound (A) are 1,4-diAm;nohutane, 1,6-diaminohexane, 2-methylpentamethylenediamine, 2,2,4(2,4,4,)-trimethylhexamethylenediamine, isophoronediamine (IPD); 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 2,5-diamino-2,5-dimethylh~Ane, 1,11-diaminoundecane or 1,12-diaminododecane.
Examples of maleic and fumaric esters which may be used for preparing the starting component (A) are dimethyl, diethyl, di-n- or -isopropyl, di-n-butyl, di-i-butyl, di-t-butyl, di-n-pentyl, di-i-pentyl, di-neopentyl, di-hexyl, di-heptyl, di-octyl and di-2-ethylhexyl maleates or the correspo~; ng fumaric esters.
The reaction of the starting compound (A) with the diamine HX-R"-XH is carried out preferably in bulk, but it is of course also possible to operate in an inert solvent, at from 50 to 150~C. If a diprimary diamine H2N-R"-NH2 is used, it is preferably carried out at a temperature of from 80 to 100~C, since at a higher temperature, the formation of a cyclic imide must be expected. The alcohol R OH which forms is distilled off from the reaction product during the reaction. The diamine HX-R"-XH involved may be a diprimary CA 0221462~ 1997-09-0~
diamine such as 1,4-diAm;nohutane, 1,6-diaminoh~Ane, 2-methylpentamethylenediamine (MPDA), 2,2,4(2,4,4)-trimethyl-1,6-diaminohexane (TMD), isophoronediamine (IPD), 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 2,5-diamino-2,5-dimethyl h~n~, l,ll-diaminoundecane or l,12-diaminododecane; a diamine contA; n; ng one primary amino group and one secondary amino group such as N-isobutyltrimethylhexamethylenediamine, N-isobutylisophoronediamine; or a disecondary diamine such as N,N'-diisobutyltrimethylh~Amethylenediamine and N,N'-diiso-propyl-IPD.
The diamine having one primary amino group and one secondary amino group suitable for the reaction with the starting compound A may be prepared according to a two stage method: in the 1st stage the diprimary diamine is co~n~ed with an aldehyde or ketone to form the Schiff base and in the 2nd stage the Schiff base is hydrogenated and separated from the starting materials, for example, by fractional distillation. In order to m; n;m; ze the production of by-product (di-Schiff base), it is necessary to work with a large excess of diamine; preferably 10 mols of the diamine are reacted with one mole of the carbonyl compound in a known mAnner. The diprimary diamines suitable for the co~ncation to form the Schiff base are, in principle, all (cyclo)aliphatic diamines, examples of which have already been listed. As the carbonyl compound to be employed for the preparation of the Schiff base, all (cyclo)aliphatic aldehydes and ketones are suitable in principle. Preference, however, CA 0221462~ 1997-09-0~
is given to the use of isobutyraldehyde, 2-ethylh~n~l, methyl ethyl ketone, diisobutyl ketone and cycloh~no~e. The disecondary diamines may be prepared using a similar method to that for the diamines just described that had one primary and one secondary amino group; the only difference is that in this case the preferred molar ratio of the diprimary diamine to carbonyl compound is not 10:1 but 1:2.
In some cases it has proven expedient to leave the mono-alcohol, which is liberated in the course of the novel process, in the reaction product rather than removing it by distillation.
The following examples illustrate the invention and are intended in no way to limit its scope.
Experimental section 1. General preparation procedure for the novel comPounds a) Preparation of the startinq compound A
The maleic ester is heated at 40~C and the diamine (H2N-R-NH2) is metered in at a rate such that the temperature does not rise above 60~C. After the end of the addition of diamine, heating is continued at 60~C for about 3 h in order to bring the reaction to completion.
b) Reaction of A with diamines A is heated with the diamine in the desired molar ratio at from 50 to 150~C until two moles of amide groups have formed per mole of diamine employed. This can be readily monitored by determ;n;ng the amine content of the reaction product. The reaction temperature is greatly dependent on the structure of the diamine employed. In CA 0221462~ 1997-09-0~
the case of the diprimary diamines, from 80~C to a m~ lm of 100~C has been found appropriate; in the case of the disecondary diamines, which are slower to react, it is necessary to work at from 130 to 150~C. The alcohol formed during the reaction is distilled off after the reaction. This is the case when the alcohols involved are relatively high-boiling; the low-boiling alcohols liberated are distilled off continuously during the actual reaction.
Diamine-maleic ester (1:2) adducts employed in the examples:
A1: 1 mol TMD + 2 mol diethyl maleate A2: 1 mol hexamethylenediamine + 2 mol dibutyl maleate A3: 1 mol 2-methylpentamethylenediamine (MPDA) + 2 mol di-2-ethylhexyl maleate Table: Composition and properties of some novel compounds Example Reactants NH2 Viscosity No. (23~C) [mmol/g] [mPa.s]
mol of A mol of diamine 1 2 A3 1 TMD 2.7 41.10 2 3 A3 1 TMD 2.5 7.10 3 4 A1 1 IPD 3.7 5.103 4 2.5 A2 1 MPDA 3.4 32.10
Polyamines cont~; n; nq ester and amide qroups The present invention relates to a group of novel polyamine cont~; n; ng an ester group and an amine group, and to a process for their preparation.
The preparation of a reaction product of a diamine and two moles of maleic ester is described in DE-A 16 70 812 as an intermediate stage in the preparation of hydatoins. The use of this aspartic acid derivative (PADE for short) as a reaction component of a polyisocyanate for preparing a coating takes place in EP 0 403 921. In EP 0 470 461, the use of the aspartic acid derivative PADE (+ polyisocyanates) is claimed as a two-component binder combination in an automative refinish. Surprisingly, the literature contains no reference to the use of the aspartic acid derivative for preparing a two-component (two pack) polyurethane (PU) adhesive. As our own experiments show, bonds produced using the PADE and a polyisocyanate exhibit only moderate tensile shear strength.
It has surprisingly been found to be possible to bring about a considerable increase in the tensile shear strength if the aspartic acid derivative employed for bo~; ng contains at least one amide group.
The present invention accordingly provides a polyamine cont~;n;ng an ester group and an amide group, of the formula:
CA 0221462~ 1997-09-0~
R 1~ R R
R'O--C--CH2~ ,CH2--C--X--R"--X--C--CH2' ,CH2--C--OR' CH--N--R--N--CH~ ,CH--N--R--N--CH~
R O fi H H- fi fi H~ H fi--OR' o O O O
where the substituents are defined as follows:
R and R" are each a divalent linear, branched or cyclic hydrocarbon radical of 4 to 18 carbon atoms, wherein the cyclic hydrocarbon radicals may be substituted with one or more C1-C4 alkyl groups, R' is an alkyl radical of 1 to 14 carbon atoms, X is NH or NR"', and R''' is an alkyl radical of 1 to 14 carbon atoms, wherein R, R' and R" may each have one or more oxygen atoms in place of a CH2 group.
The novel compound preferably has a basic amine content of from 1.5 to 4 mmol of NH2/g, an ester group content of from 3 to 7 mmol/g, more preferably from 4 to 6.5 mmol/g, an amide group content of from 0.6 to 2 mmol/g, more preferably from 0.8 to 1.7 mmol/g, and an NH functionality of from 2.5 to 4, more preferably 3. They may likewise be in admixture with up to 3 moles of compounds of the formula A
described hereinunder.
The viscosity of the novel compound at 23~C varies within a wide range, for example, from 1000 to 10 mPa.s.
The novel compound can be processed without problems, either in solvent-free form or in an inert solvent, with a polyisocyanate to form a two-pack polyurethane (PU) CA 0221462~ 1997-09-0~
coating material. A preferred field of application of the novel compound is the use as a reaction component for the preparation of two-pack polyurethane (PU) adhesive.
The present invention additionally provides a process for preparing the novel compound, which comprises reacting a product of the reaction of a diprimary diamine and maleic or fumaric ester (molar ratio 1:2) of the following formula:
1~l 1~l R'O--C--CH2, ,CH2--C--OR' CH--N--R--N--CH (A) R'O--IC H H 'C--OR' wherein R and R' are as defined above, with a diamine HX-R"-XH
contA;n;ng two primary or one primary and one secondary, or two secondary amino groups. The reaction may be carried out in such a way that from about 2 to 5 mols of the compound (A) is used per mole of the diamine.
The starting compound (A) employed in the novel process is known and is described in EP O 403 921.
The starting compound (A) employed in the novel process may be prepared in a m~nner known per se by reacting a diprimary diamine H2N-R-NH2 with 2 mol~ of maleic or fumaric ester as illustrated by the following scheme:
CA 0221462~ 1997-09-0~
Il O O
H2N--R--NH2 + 2 HC 'OR' ~ ,CH--N--R--N--CH 2 HC'C'OR R'O--ICl H H ICl--OR' o O O
(A) Examples of the diprimary diamine which may be used for preparing the compound (A) are 1,4-diAm;nohutane, 1,6-diaminohexane, 2-methylpentamethylenediamine, 2,2,4(2,4,4,)-trimethylhexamethylenediamine, isophoronediamine (IPD); 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 2,5-diamino-2,5-dimethylh~Ane, 1,11-diaminoundecane or 1,12-diaminododecane.
Examples of maleic and fumaric esters which may be used for preparing the starting component (A) are dimethyl, diethyl, di-n- or -isopropyl, di-n-butyl, di-i-butyl, di-t-butyl, di-n-pentyl, di-i-pentyl, di-neopentyl, di-hexyl, di-heptyl, di-octyl and di-2-ethylhexyl maleates or the correspo~; ng fumaric esters.
The reaction of the starting compound (A) with the diamine HX-R"-XH is carried out preferably in bulk, but it is of course also possible to operate in an inert solvent, at from 50 to 150~C. If a diprimary diamine H2N-R"-NH2 is used, it is preferably carried out at a temperature of from 80 to 100~C, since at a higher temperature, the formation of a cyclic imide must be expected. The alcohol R OH which forms is distilled off from the reaction product during the reaction. The diamine HX-R"-XH involved may be a diprimary CA 0221462~ 1997-09-0~
diamine such as 1,4-diAm;nohutane, 1,6-diaminoh~Ane, 2-methylpentamethylenediamine (MPDA), 2,2,4(2,4,4)-trimethyl-1,6-diaminohexane (TMD), isophoronediamine (IPD), 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 2,5-diamino-2,5-dimethyl h~n~, l,ll-diaminoundecane or l,12-diaminododecane; a diamine contA; n; ng one primary amino group and one secondary amino group such as N-isobutyltrimethylhexamethylenediamine, N-isobutylisophoronediamine; or a disecondary diamine such as N,N'-diisobutyltrimethylh~Amethylenediamine and N,N'-diiso-propyl-IPD.
The diamine having one primary amino group and one secondary amino group suitable for the reaction with the starting compound A may be prepared according to a two stage method: in the 1st stage the diprimary diamine is co~n~ed with an aldehyde or ketone to form the Schiff base and in the 2nd stage the Schiff base is hydrogenated and separated from the starting materials, for example, by fractional distillation. In order to m; n;m; ze the production of by-product (di-Schiff base), it is necessary to work with a large excess of diamine; preferably 10 mols of the diamine are reacted with one mole of the carbonyl compound in a known mAnner. The diprimary diamines suitable for the co~ncation to form the Schiff base are, in principle, all (cyclo)aliphatic diamines, examples of which have already been listed. As the carbonyl compound to be employed for the preparation of the Schiff base, all (cyclo)aliphatic aldehydes and ketones are suitable in principle. Preference, however, CA 0221462~ 1997-09-0~
is given to the use of isobutyraldehyde, 2-ethylh~n~l, methyl ethyl ketone, diisobutyl ketone and cycloh~no~e. The disecondary diamines may be prepared using a similar method to that for the diamines just described that had one primary and one secondary amino group; the only difference is that in this case the preferred molar ratio of the diprimary diamine to carbonyl compound is not 10:1 but 1:2.
In some cases it has proven expedient to leave the mono-alcohol, which is liberated in the course of the novel process, in the reaction product rather than removing it by distillation.
The following examples illustrate the invention and are intended in no way to limit its scope.
Experimental section 1. General preparation procedure for the novel comPounds a) Preparation of the startinq compound A
The maleic ester is heated at 40~C and the diamine (H2N-R-NH2) is metered in at a rate such that the temperature does not rise above 60~C. After the end of the addition of diamine, heating is continued at 60~C for about 3 h in order to bring the reaction to completion.
b) Reaction of A with diamines A is heated with the diamine in the desired molar ratio at from 50 to 150~C until two moles of amide groups have formed per mole of diamine employed. This can be readily monitored by determ;n;ng the amine content of the reaction product. The reaction temperature is greatly dependent on the structure of the diamine employed. In CA 0221462~ 1997-09-0~
the case of the diprimary diamines, from 80~C to a m~ lm of 100~C has been found appropriate; in the case of the disecondary diamines, which are slower to react, it is necessary to work at from 130 to 150~C. The alcohol formed during the reaction is distilled off after the reaction. This is the case when the alcohols involved are relatively high-boiling; the low-boiling alcohols liberated are distilled off continuously during the actual reaction.
Diamine-maleic ester (1:2) adducts employed in the examples:
A1: 1 mol TMD + 2 mol diethyl maleate A2: 1 mol hexamethylenediamine + 2 mol dibutyl maleate A3: 1 mol 2-methylpentamethylenediamine (MPDA) + 2 mol di-2-ethylhexyl maleate Table: Composition and properties of some novel compounds Example Reactants NH2 Viscosity No. (23~C) [mmol/g] [mPa.s]
mol of A mol of diamine 1 2 A3 1 TMD 2.7 41.10 2 3 A3 1 TMD 2.5 7.10 3 4 A1 1 IPD 3.7 5.103 4 2.5 A2 1 MPDA 3.4 32.10
Claims (13)
1. A polyamine containing an ester group and an amide group, of the following formula:
(I) (wherein R and R" are each a divalent, linear, branched or cyclic hydrocarbon radical of 4 to 18 carbon atoms, wherein the cyclic hydrocarbon radical may be substituted with one or more C1-C4 alkyl groups, R' is an alkyl radical of 1 to 14 carbon atoms, X is NH or NR''', and R''' is an alkyl radical of 1 to 14 carbon atoms, and wherein R, R' and R" may each have 1 or more oxygen atoms in place of a CH2 group).
(I) (wherein R and R" are each a divalent, linear, branched or cyclic hydrocarbon radical of 4 to 18 carbon atoms, wherein the cyclic hydrocarbon radical may be substituted with one or more C1-C4 alkyl groups, R' is an alkyl radical of 1 to 14 carbon atoms, X is NH or NR''', and R''' is an alkyl radical of 1 to 14 carbon atoms, and wherein R, R' and R" may each have 1 or more oxygen atoms in place of a CH2 group).
2. A polyamine as claimed in claim 1 wherein R and R"
are selected from divalent, linear, branched or cyclic hydrocarbon radicals of 4 to 18 carbon atoms.
are selected from divalent, linear, branched or cyclic hydrocarbon radicals of 4 to 18 carbon atoms.
3. A polyamine as claimed in claim 1, wherein the cyclic hydrocarbon radical as R or R" is substituted with a group selected from methyl, ethyl, propyl and butyl.
4. A polyamine as claimed in claim 1, wherein R is a hydrocarbon radical derived from a diamine selected from 1,4-diaminobutane, 1,6-diaminohexane, 2-methylpentamethylene-diamine, 2,2,4(2,4,4)-trimethyl-1,6-diaminohexane, isophoronediamine (IPD); 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 2,5-diamino-2,5-dimethylhexane, 1,11-diaminoundecane and 1,12-diaminodo-decane.
5. A polyamine as claimed in claim 1 or 4, wherein R"
is a hydrocarbon radical derived from a diamine selected from 1,4-diaminohutane, 1,6-diaminohexane, 2-methylpentamethylene-diamine, 2,2,4(2,4,4)-trimethyl-1,6-diaminohexane, isophoronediamine (IPD); 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 2,5-diamino-2,5-dimethylhexane, 1,11-diaminoundecane and 1,12-diaminodo-decane.
is a hydrocarbon radical derived from a diamine selected from 1,4-diaminohutane, 1,6-diaminohexane, 2-methylpentamethylene-diamine, 2,2,4(2,4,4)-trimethyl-1,6-diaminohexane, isophoronediamine (IPD); 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 2,5-diamino-2,5-dimethylhexane, 1,11-diaminoundecane and 1,12-diaminodo-decane.
6. A polyamine as claimed in any of claims 1 to 4, wherein the radical X-R"-X is derived from a diamine selected from N-isobutyltrimethylhexamethylenediamine, N-isobutyl-isophoronediamine, N,N'-diisobutyltrimethylhexamethylene-diamine and N,N'-diisopropyl-IPD.
7. A polyamine as claimed in any of claims 1 to 5, wherein R' is a linear or branched alkyl radical selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, neopentyl, hexyl, heptyl, and 2-ethylhexyl.
8. A polyamine containing ester groups and amide groups, as claimed in any one of claims 1 to 7, in admixture with up to 3 mols of a compound of the formula A:
(A) wherein R and R' are as defined in any one of claims 1 to 7.
(A) wherein R and R' are as defined in any one of claims 1 to 7.
9. A process for preparing the polyamine as defined in any one of claims 1 to 7, which comprises reacting a compound of general formula (A) (A) (wherein R and R' are as defined in any one of claims 1 to 7), with a diamine of the formula HX-R"-XH (wherein R" and X are as defined in any one of claims 1 to 7), at a molar ratio of from about 2 to about 5 moles of the compound (A) to 1 mole of the diamine, at a temperature of from about 50°C to about 150°C.
10. The process of claim 9, wherein the diamine is a diprimary diamine H2N-R"-NH2 and the reaction is carried out at 80 to 100°C.
11. The process of claim 10, wherein the diamine is a disecondary diamine HNR'''-R"-R'''NH and the reaction is carried out at 130 to 150°C.
12. The process of any one of claims 9 to 11, wherein the compound of the formula (A) is produced by reacting a diprimary diamine H2-R-NH2 (wherein R has the meaning given in claim 9) with a maleic or fumaric ester, R'O-CO-CH=CH-CO-OR' (wherein R' has the meaning given in claim 9), in a molar ratio of 1 mole of the diamine to 2 mole of the ester.
13. The use of a polyamine as claimed in any of claims 1 to 8 as a component for two-pack polyurethane adhesive.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19636529.5 | 1996-09-09 | ||
| DE1996136529 DE19636529A1 (en) | 1996-09-09 | 1996-09-09 | Poly:amine compounds with ester and amide groups |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2214625A1 true CA2214625A1 (en) | 1998-03-09 |
Family
ID=7805025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2214625 Abandoned CA2214625A1 (en) | 1996-09-09 | 1997-09-05 | New polyamines containing ester and amide groups |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH10101632A (en) |
| CA (1) | CA2214625A1 (en) |
| DE (1) | DE19636529A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019154535A1 (en) * | 2018-02-09 | 2019-08-15 | Glue Tec Industrieklebstoffe Gmbh & Co. Kg | Two-component structural adhesives |
| US11999881B2 (en) | 2018-02-09 | 2024-06-04 | Glue Tec Industrieklebstoffe Gmbh & Co. Kg | Two-component structural adhesives |
-
1996
- 1996-09-09 DE DE1996136529 patent/DE19636529A1/en not_active Withdrawn
-
1997
- 1997-09-05 CA CA 2214625 patent/CA2214625A1/en not_active Abandoned
- 1997-09-09 JP JP24391897A patent/JPH10101632A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019154535A1 (en) * | 2018-02-09 | 2019-08-15 | Glue Tec Industrieklebstoffe Gmbh & Co. Kg | Two-component structural adhesives |
| EP3749730B1 (en) | 2018-02-09 | 2023-01-18 | Glue Tec Industrieklebstoffe GmbH & Co. Kg | Two-component structural adhesives |
| US11999881B2 (en) | 2018-02-09 | 2024-06-04 | Glue Tec Industrieklebstoffe Gmbh & Co. Kg | Two-component structural adhesives |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19636529A1 (en) | 1998-03-12 |
| JPH10101632A (en) | 1998-04-21 |
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