EP3350249A1 - Nouvelles amines biosourcées - Google Patents

Nouvelles amines biosourcées

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Publication number
EP3350249A1
EP3350249A1 EP16762806.4A EP16762806A EP3350249A1 EP 3350249 A1 EP3350249 A1 EP 3350249A1 EP 16762806 A EP16762806 A EP 16762806A EP 3350249 A1 EP3350249 A1 EP 3350249A1
Authority
EP
European Patent Office
Prior art keywords
group
amine
amidoamine
range
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16762806.4A
Other languages
German (de)
English (en)
Inventor
Sophie PUTZIEN
Olivier FLEISCHEL
Bernd Bruchmann
Andreas Kuenkel
Radoslaw Kierat
Rolf Muelhaupt
Matteo GIGLI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3350249A1 publication Critical patent/EP3350249A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • 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
    • C07C237/06—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 having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes

Definitions

  • the present invention relates to a process for the preparation of an amidoamine by reacting a tris-acid derivative (I) with at least one amine (A), wherein the at least one amine (A) is selected from the group consisting of diethylenetriamine and a diamine (II ).
  • the molar ratio of the triklarederivats (I) to the at least one amine (A) is in the range of 1: 2 to 1: ⁇ 3.
  • the present invention relates to the amidoamine as such, as well as the use of the amidoamine according to the invention as a crosslinker.
  • crosslink polymer chains In polymer chemistry, it is often necessary to crosslink polymer chains in order to change the properties of a polymer in a targeted manner.
  • the properties to be changed include in particular the hardness, the toughness, the melting point and the solubility of the polymer.
  • the crosslinking can be carried out during the preparation of the polymers by the use of at least one polyfunctional monomer, it is also possible to crosslink already prepared polymer chains by a suitable crosslinker.
  • Crosslinkers are also referred to as hardeners.
  • a crosslinker turns three polymer networks into three-dimensional network structures.
  • the prior art describes various processes for the preparation of suitable crosslinkers and the use of these crosslinkers for crosslinking polymer chains. M. Bahr et al, Green Chem.
  • Non-isocyanate-containing oligo- and polyurethanes are prepared from cyclic carbonates based on terpenes such as limonene and amines such as 1,4-butanediamine, 1,6-hexamethylenediamine, isophoronediamine and 1,8-octamethylenediamine.
  • crosslinked isocyanate-free oligo- and polyurethanes can be obtained by reaction with triamines.
  • the crosslinker used is, for example, an amidoamine prepared from triethyl citrate and 1,6-hexamethylenediamine or 1,12-dodecamethylenediamine. To prepare the trifunctional amidoamine, the triethyl citrate is reacted with the diamine in a molar ratio of 1:21.
  • a disadvantage of the process described is that the resulting crosslinked oligo- and polyurethanes are extremely brittle.
  • the amidoamines used as crosslinkers have a relatively high melting point, so that the amidoamines can only be used as crosslinkers at either high Temperatures so that they are in liquid form or by being dissolved in a solvent.
  • M. Fleischer et al, Green Chem. 2013, 15, 934-942 also describe a process for the preparation of polyurethanes without isocyanate and their crosslinking with an amidoamine.
  • the polyurethanes are prepared starting from cyclic carbonates, e.g. based on pentaerythritol glycidyl ethers, which are reacted with a diamine.
  • the amidoamine which serves as a crosslinker, is prepared by reacting triethyl citrate with hexamethylenediamine using 7.5 equivalents of hexamethylenediamine.
  • the product obtained in the reaction contains the amidoamine and excess hexamethylenediamine. This mixture is then used to crosslink the polyurethane.
  • a disadvantage of the described method is that for curing a mixture of hexamethylenediamine and the amidoamine is mandatory. This means that both the hexamethylenediamine and the amidoamine can react with the cyclic carbonate, so that a targeted control of the crosslinking is difficult. If only the amidoamine is to be used in the process described, it is imperative that the hexamethylenediamine is previously removed, which makes the process extremely complicated and expensive.
  • WO 2012/171659 also describes the preparation of isocyanate-free polyurethanes. These are prepared starting from a terpene derivative containing at least two cyclic carbonate groups and an amine.
  • the amine used may be an amidoamine having a functionality of> 2.
  • the amidoamine is prepared starting from a citric acid ester and a diamine, which is selected from 1, 4-diaminobutane, 1, 5-diaminopentane and 1, 6-diaminohexane.
  • the citric acid ester is used in a molar ratio of 1: 3 to the amidoamine.
  • the amidoamine is therefore a trifunctional amidoamine, thus has an amine functionality of 3.
  • CN 101 328 267 describes the production of biodegradable polyamide-imides.
  • a citrate is reacted with an aliphatic diamine, wherein the molar ratio is in the range of 1: 0.2 to 1: 5.
  • the diamines used are preferably hexanediamine and butanediamine. It is obtained a polyamide, which is then reacted in a second step to a polyamide-imide.
  • CN 101 497 695 also describes the preparation of polyamide-imides.
  • the preparation is carried out starting from citric acid esters and aliphatic diamines in a molar ratio of 1: 0.1 to 1:10. Preference is given to hexanediamine and Butandiamine used as diamines. A polyamide is obtained, which is subsequently set to the polyamideimide.
  • a disadvantage of all the processes described above for the preparation of an amidoamine as crosslinker is that the amidoamines are usually obtained in solid form. As a result, they are difficult to dose and may need to be diluted for use as a crosslinker in order to be able to dose them in liquid form. If they are not to be diluted, the crosslinking must be carried out at relatively high temperatures so that the amidoamines are in liquid form and can also be metered in liquid form.
  • Another disadvantage is that very brittle crosslinked polyurethanes are often obtained by the amidoamines used as crosslinkers in the prior art.
  • the amidoamines described in the prior art have a relatively low amine functionality, which can lead to low crosslinking.
  • the synthesis and purification of the pure amidoamines described in the prior art is very complicated and expensive, since always a large excess of the amine component is needed, which must be removed from the system again after successful implementation.
  • the present invention was thus based on the object of providing a process for the preparation of amidoamines which are suitable for use as crosslinkers of polymers.
  • the method should be as simple and inexpensive to carry out and not or only to a reduced extent have the disadvantages of the methods described in the prior art described above.
  • This object is achieved by a process for the preparation of an amidoamine by reacting a tris-acid derivative of the general formula (I)
  • X 1 is selected from the group consisting of Cl, Br, I and OR 1 ;
  • X 2 is selected from the group consisting of Cl, Br, I and OR 2 ; is selected from the group consisting of Cl, Br, I and OR 3 , wherein R 1 , R 2 , R 3 are independently selected from the group consisting of hydrogen and unsubstituted or at least monosubstituted C 1 -C 2 o-alkyl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, and CC 10 alkyl;
  • R 4 is an unsubstituted or at least monosubstituted C 1 -C 2 o-alkyl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, and CC 10 alkyl; with at least one amine (A) selected from the group consisting of diethylenetriamine and a diamine of the general formula (II)
  • R 5 is a branched C 3 -C 31 -alkyl or an unbranched C n -alkyl, where n is an odd integer in the range of 3 to 31, characterized in that the molar ratio of the tris-acid derivative (I) to the at least one Amine (A) is in the range of 1: 2 to 1: ⁇ 3.
  • amidoamine prepared according to the invention generally has no crystalline domains and has a low glass transition temperature T G.
  • the glass transition temperature T G is usually at temperatures below the temperatures at which the amidoamine is metered to be used as a crosslinker in a crosslinking reaction. This means that the amidoamine according to the invention is usually flowable at the temperatures at which it is metered. This makes the dosage of the amidoamine prepared according to the invention very simple for use in a crosslinking reaction.
  • the process of the invention can be carried out quickly and the presence of a catalyst is not absolutely necessary, which makes the process according to the invention extremely cost-effective.
  • the amidoamine according to the invention can be used as crosslinker. It has low toxicity, is at least partially biodegradable and is based on renewable resources. In addition, it has a good thermal and chemical stability, which is also advantageous for use as a crosslinker.
  • Triacid derivative (I) In the present invention, a triacid derivative (I) is reacted. In the context of the present invention, "a triacid derivative (I)” is understood to mean both exactly one tris acid derivative (I) and a mixture of two or more tris acid derivatives (I).
  • tris acid derivative (I) includes both the triacid itself and compounds derived therefrom, provided that they can be described by the general formula (I).
  • X 1 is selected from the group consisting of Cl, Br, I and OR 1 ;
  • X 2 is selected from the group consisting of Cl, Br, I and OR 2
  • X 3 is selected from the group consisting of Cl, Br, I and OR 3 , where R 1 , R 2 , R 3 are independently selected from the group consisting of hydrogen and unsubstituted or at least monosubstituted C 1 -C 2 o-alkyl, where the substituents are selected from the group consisting of F, Cl, Br, OH, CN and CC 10 alkyl
  • R is selected from the group consisting of hydrogen and
  • R 4 is an unsubstituted or at least monosubstituted
  • C 20 alkyl wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN and CC 10 alkyl.
  • R 4 denotes an acyl group.
  • Acyl groups are known to the person skilled in the art.
  • the substituents of the triacid derivative (I) have the following meaning:
  • X 1 is selected from the group consisting of Cl, Br and OR 1 ;
  • X 2 is selected from the group consisting of Cl, Br and OR 2 ;
  • X 3 is selected from the group consisting of Cl, Br and OR 3 , where
  • R 1 , R 2 , R 3 are independently selected from the group consisting of hydrogen and unsubstituted or at least monosubstituted C "
  • R is selected from the group consisting of hydrogen and
  • R 4 is an unsubstituted or at least monosubstituted C 1-6 -alkyl, where the substituents are selected from the group consisting of F, Cl, Br, OH, CN and C 1 -C 8 -alkyl.
  • the substituents of the triklarederivats (I) have the following meaning: X 1 is OR 1 ;
  • X 2 is OR 2 ;
  • X 3 is OR 3 , where
  • R 1 , R 2 , R 3 are independently selected from the group consisting of hydrogen and unsubstituted C 1 -C 4 alkyl;
  • R is hydrogen
  • X 1 is OR 1 ;
  • X 2 is OR 2 ;
  • X 3 is OR 3 , where R 1 , R 2 , R 3 are the same and are selected from the group consisting of hydrogen, methyl and ethyl;
  • R is hydrogen
  • the triacid derivative (I) is citric acid.
  • the lUPAC name of citric acid is 2-hydroxypropane-1,2,3-tricarboxylic acid. It carries the CAS number 77-92-9. If X 1 is OR 1 , X 2 is OR 2 and X 3 is OR 3 and R 1 , R 2 and R 3 are all three methyl and R is hydrogen, the tris acid derivative (I) is trimethyl citrate (trimethyl citrate).
  • the IUPAC name of trimethyl citric acid is trimethyl 2-hydroxypropane-1,2,3-tricarboxylate.
  • the tris acid derivative (I) is triethyl citrate (triethyl citrate).
  • the lUPAC name of citric acid triethyl ester is triethyl 2-hydroxypropane-1,2,3-tricarboxylate.
  • He carries the CAS number 77-93-0.
  • the tris acid derivative (I) is most preferably selected from the group consisting of citric acid, trimethyl citric acid and citric acid triethyl ester.
  • the present invention thus also provides a process in which the tris acid derivative (I) is selected from the group consisting of citric acid, trimethyl citric acid and triethyl citrate.
  • citric anhydride can be used as the tris acid derivative. This is known to the skilled person as such.
  • at least one amine (A) is understood to mean both exactly one amine (A) and also a mixture of two or more amines (A).
  • the at least one amine (A) is selected from the group from diethylenetriamine and a diamine (II)
  • the at least one amine (A) is preferably a diamine (II).
  • the present invention thus also provides a process in which the at least one amine (A) is a diamine (II).
  • R 5 is a branched C 3 -C 31 alkyl or an unbranched C n alkyl, wherein n is an odd integer in the range of 3 to 31.
  • the substituents of diamine (II) have the following meaning: R 5 is a branched C 3 -C 2 o-alkyl or an unbranched C n -alkyl, wherein n is an odd integer in the range of 3 to 21.
  • R 5 is a branched C 3 -C 3 -alkyl or an unbranched C n -alkyl, where n is an odd integer in the range 3 to 13
  • the present invention thus also provides a process in which the amine (A) used is a diamine of the general formula (II) in which
  • R5 is a branched C 3 -C 13 alkyl or a straight-chain C n alkyl, where n is an odd integer in the range of 3 to 13.
  • R 5 is an unbranched C n -alkyl, wherein, n is an odd number in the range of 3 to 31, preferably in the range of 3 to 21 and especially preferred in
  • Range is 3 to 13.
  • R 5 is a branched C 3 -C 31 -alkyl, preferably a branched C 3 -C 2 o-alkyl and particularly preferably a branched C 3 -C 13 -alkyl.
  • the at least one amine (A) is furthermore preferably selected from the group consisting of diethylenetriamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 2,2-dimethyl-1,3-propanediamine, 1, 5-diaminopentane, 1, 5-diamino-2-methylpentane, 1, 7-diaminoheptane, 2-butyl-2-ethyl-1, 5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine and 2,4,4-trimethyl- 1, 6-hexanediamine.
  • the present invention thus also provides a process in which the at least one amine (A) is selected from the group consisting of diethylenetriamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 2,2-dimethyl-1, 3 propanediamine, 1, 5-diaminopentane, 1, 5-diamino-2-methylpentane, 1, 7-diaminoheptane, 2-butyl-2-ethyl-1, 5-pentanediamine, 2,2, 4-trimethyl-1, 6 hexanediamine and 2,4,4-trimethyl-1,6-hexanediamine.
  • the at least one amine (A) is selected from the group consisting of diethylenetriamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 2,2-dimethyl-1, 3 propanediamine, 1, 5-diaminopentane, 1, 5-diamino-2-methylpentane, 1, 7-diaminoheptane
  • the at least one amine (A) is selected from the group consisting of 1, 2-diaminopropane, 1, 3-diaminopropane, 2,2-dimethyl-1, 3-propanediamine, 1, 5-diaminopentane, 1, 5-diamino-2-methylpentane, 1, 7-diaminoheptane, 2-butyl-2-ethyl-1, 5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine and 2,4,4-trimethyl- 1, 6-hexanediamine.
  • the at least one amine (A) is selected from the group consisting of 1, 3-diaminopropane, 1, 5-diaminopentane and 1, 7-diaminoheptane.
  • the at least one amine (A) is selected from the group consisting of 1, 2-diaminopropane, 2,2-dimethyl-1,3-dipropanediamine, 1, 5-diamino-2-methylpentane, 2-butyl 2-ethyl-1, 5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine and 2,4,4-trimethyl-1,6-hexanediamine.
  • unsubstituted or at least mono-substituted C 1 -C 2 o alkyl refers to saturated and unsaturated hydrocarbons having a free valence (radical) and from 1 to 20 carbon atoms are understood in the context of the present invention.
  • the hydrocarbons can be linear or cyclic.
  • branched C 3 -C 31 -alkyl is understood as meaning a saturated or unsaturated hydrocarbon having a free valency (radical) and from 3 to 31 carbon atoms which has at least one branch, ie at least one alkyl group as substituent
  • the number of carbon atoms refers to the total number of carbon atoms in the C 3 -C 31 -alkyl, that is to say the sum of the carbon atoms in the hydrocarbon and the at least one alkyl group as substituent
  • the branched C 3 -C 31 -alkyl has It preferably has no substituents other than an alkyl group, corresponding statements apply to "branched C 3 -C 2 0-alkyl" and "branched C 3 -C 13 alkyl ".
  • unbranched C n alkyl is a saturated or unsaturated hydrocarbon having a free valence (radical) and n carbon atoms
  • the straight chain C is understood in the context of the present invention, which has no branching, so no alkyl group as a substituent.
  • N alkyl preferably has also no substituents that are different from an alkyl group.
  • An unbranched Cn-alkyl in the context of the present invention is therefore preferably unsubstituted.
  • “Odd integer” means an integer that is not divisible without remainder by 2. Examples of these are 3, 5, 7, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29 and 31.
  • the tris-acid derivative (I) is reacted with the at least one amine (A) for the preparation of the amidoamine.
  • the reaction can be carried out by all methods known to the person skilled in the art.
  • the reaction of the tris-acid derivative (I) with the at least one amine (A) can be carried out, for example, in the presence of a solvent. It is also possible that the reaction takes place without a solvent.
  • the reaction of the tris-acid derivative (I) with the at least one amine (A) preferably takes place in the absence of a solvent.
  • reaction of the triklarederivats (I) with the at least one amine (A) takes place in the presence of a catalyst which catalyzes the reaction of the tri-acid derivative (I) with the at least one amine (A).
  • the reaction preferably takes place in the absence of a catalyst.
  • reaction of the tris-acid derivative (I) with the at least one amine (A) can take place in all reactor forms known to the person skilled in the art.
  • Suitable reactors are, for example, stirred tank reactors, stirred tank cascades or tube reactors.
  • the reaction of the tris-acid derivative (I) with the at least one amine (A) can take place at any temperature.
  • the reaction of the triklarederivats (I) with the at least one amine (A) takes place at a temperature T in the range of 20 to 200 ° C.
  • the reaction takes place at a temperature in the range from 40 to 120 ° C., and particularly preferably at a temperature in the range from 50 to 100 ° C.
  • the present invention thus also provides a process in which the reaction of the tris-acid derivative (I) with the at least one amine (A) takes place at a temperature T in the range from 20 to 200 ° C.
  • the pressure during the reaction of the triklarederivats (I) with the at least one amine (A) may be arbitrary.
  • the pressure during the reaction of the triklarederivats (I) with the at least one amine (A) in the range of 0.1 mbar to 10 bar, preferably in the range of 1 mbar to 2 bar and particularly preferably in the range of 750 mbar 1, 5 bar.
  • the reaction of the tris-acid derivative (I) with the at least one amine (A) can be carried out for any desired time.
  • the time for the reaction of the tris-acid derivative (I) with the at least one amine (A) is in the range of 0.5 to 18 hours, preferably in the range of 1 to 10 hours and more preferably in the range of 2 to 8 hours.
  • the tris-acid derivative (I) can be initially introduced into the reactor, then brought to the temperature T at which the reaction takes place and then the at least one amine (A) is added , It is likewise possible first to introduce the at least one amine (A) into the reactor and bring it to a temperature T at which the reaction takes place, and then to add the tris acid derivative (I). Moreover, it is possible to introduce the triacid derivative (I) and the at least one amine (A) together in a reactor, optionally with stirring, and then bring to the temperature T at which the reaction takes place.
  • the triacid derivative (I) and the at least one amine (A) are preferably introduced together in a reactor and brought to the temperature T with stirring, at which the reaction takes place.
  • the reaction during the reaction of the tris-acid derivative (I) with the at least one amine (A) is known to those skilled in the art.
  • one of the amino groups (NH 2 group) of the at least one amine (A) reacts with one of the COX 1 , COX 2 or COX 3 groups of the tris-acid derivative (I) to obtain an amide group.
  • X 1 H, X 2 H or X 3 H is split off.
  • the group to which the amino group of the at least one amine (A) reacts is, for example, an ester group, an alcohol is split off. If the group with which the amino group of the at least one amine (A) reacts is a carboxylic acid group, water is split off.
  • the alcohol or water is usually removed after or during the reaction of the tri-acid derivative (I) with the at least one amine (A).
  • the alcohol or water can be removed by all methods known to those skilled in the art, for example by distillation or by adding a drying agent.
  • the water or alcohol is removed by distillation, more preferably by distillation at reduced pressure.
  • the molar ratio of the tris-acid derivative (I) to the at least one amine (A) is in the range from 1: 2 to 1: ⁇ 3, preferably the molar ratio of the tris-acid derivative (I) to the at least one amine (A) is in the range from 1: 2.4 to 1: 2.8.
  • the present invention thus also provides a process in which the molar ratio of the tris-acid derivative (I) to the at least one amine (A) is in the range from 1: 2.4 to 1: 2.8.
  • the molar ratio of the tris-acid derivative (I) to the at least one amine (A) relates to the molar ratio of the tris-acid derivative (I) to the at least one amine (A) before the reaction, ie before the tris-acid derivative (I) has reacted with the at least one amine (A).
  • the amidoamine is formed according to the invention.
  • the tris-acid derivative (I) reacts with the at least one amine (A) to obtain the amidoamine.
  • the amidoamine thus contains the tris acid derivative (I) and the at least one amine (A) in reacted form (converted form).
  • the amidoamine thus contains building units derived from the tris-acid derivative (I) and building units derived from the at least one amine (A).
  • the amidoamine is preferably obtained in the reaction as an oligomer.
  • Oligomers are formed when an amino group (NH 2 group) of the at least one amine (A) reacts with a tris-acid derivative (I) and then a second amino group of the at least one amine (A) reacts with a second tris-acid derivative (I), which in turn can react with a further at least one amine (A).
  • an oligomer of the amidoamine is understood to mean that the amidoamine is in the range from 3 to 280 structural units derived from the at least one amine (A) and in the range from 1 to 120 structural units derived from the tris acid derivative ( I) contains.
  • an oligomer of the amidoamine in the range of> 3 to 140 building units derived from the at least one amine (A) and in the range of 1 to 60 building units derived from the tris-acid derivative (I). More preferably, an oligomer of the amidoamine in the range of 4 to 15 building units derived from the at least one amine (A) and in the range of 1 to 6 building units derived from the triacid derivative (I). More preferably, an oligomer of the amidoamine in the range of 4 to 12 building units derived from the at least one amine (A) and in the range of 1 to 5 building units derived from the tris-acid derivative (I).
  • the amidoamine prepared according to the invention preferably contains no crystalline constituents.
  • the amidoamine is thus preferably amorphous. This means that the amidoamine according to the invention preferably has no melting temperature.
  • the glass transition temperature T G of the amidoamine according to the invention is preferably at most at room temperature (20 ° C). For example, the glass transition temperature T G of the amidoamine is in the range of -40 to 20 ° C.
  • the present invention thus also provides a process in which the amidoamine has a glass transition temperature T G in the range from -40 to 20 ° C.
  • the amidoamine according to the invention is therefore preferably flowable at room temperature (20 ° C.).
  • Flowable in the context of the present invention means that the amidoamine has a glass transition temperature T G at or below room temperature (20 ° C.) and / or can be pumped by means of conventional pumps at temperatures between 20 ° C. and 80 ° C.
  • liquid “and” flowable are used synonymously in the context of the present invention and therefore have the same meaning.
  • the amidoamine according to the invention therefore usually has a viscosity in the range from 1,000 to 1,000,000 mPas, preferably in the range from 1,000 to 200,000 mPas and particularly preferably in the range from 1000 to 100,000 mPas, measured at 60 ° C. with an Anton Paar Physica MCR 301 Rheometer with plate-plate geometry, a shear rate of 1 / s, 6 sec / measuring point, 20 measuring points, 1 mm gap width.
  • the present invention thus also provides a process in which the amidoamine has a viscosity in the range from 1,000 to 1,000,000 mPas, measured at 60 ° C.
  • the amidoamine according to the invention preferably has a functionality in the range from 3 to 40, preferably in the range from 3 to 21 and particularly preferably in the range from 3 to 11.
  • the amidoamine according to the invention has, for example, a number average molecular weight M n in the range from 500 to 30 000 g / mol, preferably in the range from 800 to 20 000 g / mol and particularly preferably in the range from 1000 to 15 000 g / mol as determined by gel permeation chromatography (GPC ) under the use of a Waters Alliance 2695 Separation Module with Shodex OHpak SB-804HQ, SB-802, 5HQ (300x8.0mm) column and 0.3 mol / L sodium acetate, pH 4.5 (adjusted with acetic acid) as eluent, flow rate: 0.5 mL / min; Injection: 50 ⁇ _, detector: Waters Refractive Index (Rl) 2410, calibration: Pullulan or PEG / PEO.
  • M n number average molecular weight in the range from 500 to 30 000 g / mol, preferably in the range from 800 to 20 000 g / mol and
  • the present invention thus also provides a process in which the amidoamine has a weight-average molecular weight M w in the range from 500 to 30,000 g / mol.
  • the present invention further provides a process in which the amidoamine has a number average molecular weight M n in the range of 500 to 30,000 g / mol.
  • the polydispersity of the amidoamine according to the invention is, for example, in the range from 1.1 to 20, preferably in the range from 1.3 to 10 and particularly preferably in the range from 1.5 to 5. Under polydispersity, the quotient of the weight-average molecular weight M w and number average molecular weight M n understood.
  • the present invention also provides an amidoamine obtainable by the process according to the invention.
  • amidoamine according to the invention can be used, for example, as a crosslinker, for example in the preparation of polyaddition or polycondensation polymers.
  • the present invention thus also relates to the use of the amidoamine according to the invention as crosslinker.
  • the amidoamine according to the invention can be used as crosslinker in all reactions known to the person skilled in the art, in which amines are suitable as crosslinkers.
  • amidoamine according to the invention is preferably used as crosslinker for thermosetting curable resin systems.
  • thermosetting curable resin systems are known to those skilled in the art.
  • thermoset curable resin systems are selected from the group consisting of thermosetting curable isocyanate resin systems, thermosetting curable urethane resin systems, thermosetting epoxy resin systems, thermosetting polyester resin systems, thermosetting curable polyamide resin systems and thermosetting curable carbonate resin systems.
  • thermosetting curable resin systems are selected from the group consisting of thermosetting curable isocyanate resin systems, thermosetting curable urethane resin systems, thermosetting epoxy resin systems, thermosetting polyester resin systems thermosetting polyamide resin systems and thermoset curable carbonate resin systems.
  • thermosetting resin systems are known to those skilled in the art.
  • the tris acid derivative (I) was triethyl citrate (triethyl citrate,> 99%, FCC, Sigma Aldrich).
  • amine (A) - 1,5-diaminopentane (pentamethylenediamine, PMDA)
  • TMDA 1, 3-diaminopropane
  • THDA 2,2,4-trimethyl-1,6-hexanediamine
  • Example 8 the trisaur derivative (I) was reacted with the amine (A) indicated in Table 1 a in the molar ratio (trisauric derivative (I) to amine (A)) in a glass flask equipped with stirrer, descending Cooler and receiver, provided heated to the temperature indicated in Table 1 a
  • Viscosity of the obtained amidoamine determined at 60 ° C with an Anton Paar Physica MCR 301 rheometer with plate-plate geometry, shear rate 1 / s, 6 s / measuring point, 20 measuring points, 1 mm gap width. weight average and number average molecular weight as determined by gel permeation chromatography (GPC) using a Waters Alliance 2695 Separation Module with Shodex OHpak SB-804HQ, SB-802.5HQ (300x8.0 mm) column and 0.3 mol / L sodium acetate, pH 4, 5 (adjusted with acetic acid) as eluent.
  • GPC gel permeation chromatography
  • T G glass transition temperatures

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Abstract

La présente invention concerne un procédé de production d'une amidoamine par mise en réaction d'un dérivé de triacide (I) avec au moins une amine (A), ladite au moins une amine (A) étant choisie dans le groupe constitué par triamine de diéthylène et une diamine (II). Le rapport molaire du dérivé de triacide (I) et de l'au moins une amine (A) se situe dans la plage de 1/2 à 1/<3. La présente invention concerne en outre l'amidoamine en tant que telle, ainsi que l'utilisation de l'amidoamine selon l'invention en tant qu'agent de réticulation.
EP16762806.4A 2015-09-16 2016-09-07 Nouvelles amines biosourcées Withdrawn EP3350249A1 (fr)

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EP3802665B1 (fr) 2018-06-06 2023-07-19 Basf Se Polyamidoamines alcoxylées utilisées comme agents dispersants
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