CH715224B1 - Process for the preparation of a terpendiamine. - Google Patents

Abstract

The present invention relates to processes for the preparation of a terpendiamine.

Description

Description: The present invention relates to processes for the preparation of a terpendiamine.

In order to conserve fossil resources and reduce greenhouse gas emissions, there is great interest in replacing conventional plastics with those that can be produced from renewable raw materials. Conventional plastics include polyamides. These polyamides are formed by linking bifunctional monomers with amino groups and, preferably activated or non-activated, carboxyl groups. Both diamines can be reacted with dicarboxylic acids and amino acids with amino acids. In the latter case, the amino group and the carboxyl group are both functional groups required for linking in the same molecule. Among other things, lactams, such as ε-caprolactam, can be used to produce polyamides by ring-opening polymerization. Two industrially important lactams that are used for ring opening polymerization are ε-caprolactam for the production of polyamide-6 and laurolactam for the production of polyamide-12.

Ε-Caprolactam is manufactured industrially from cyclohexanone and laurolactam from cyclododecanone. The ketone is first converted to the oxime and this oxime is then converted to the lactam by a Beckmann rearrangement. Alternatively, the ketone is converted to the lactam in a single reaction, the oxime formation taking place in situ.

Lactams from Campher and Menthon have been described in the literature (Kumar, Med. Chem. Res. 2012, page 531). The lactams from a-pinene and 3-carene are also known from the literature (R.E. Gawley, Org. React. 1988, 35,1). Lochinski et al. (Tetrahedron: Asymmetry, 2000, 11, 1295) discloses the lactam from 3-carene and the ring-opened aminocarboxylic acid produced therefrom.

There is a need in the prior art for starting materials for the production of polyamides from renewable raw material sources.

The present disclosure relates to a process for the production of polyamides, renewable raw materials being used as starting compounds. In particular, the polyamide produced in this way should have improved product properties, preferably improved transparency and / or strength and / or toughness, than polyamides known from the prior art. In particular, the petroleum-based plastics are to be replaced by polyamides based on renewable raw materials, that is to say bio-based, the polyamides based on renewable raw materials advantageously having improved product properties. The polyamides based on renewable raw materials preferably have at least one, preferably several, product properties which are selected from improved transparency, higher strength and higher toughness - compared to petroleum-based polyamides.

[0007] The object of the present invention is achieved by the teaching of the independent claims.

[0008] A method for producing a polyamide is disclosed, the method comprising the following steps:

a) providing at least one terpene lactam,

b) polymerizing the at least one terpene lactam with ring opening, so that a polyamide, preferably a homopolyamide or a copolyamide, is obtained and

c) obtaining the polyamide, preferably the homopolyamide or the copolyamide, containing at least one ring-opened terpene lactam.

[0009] The term "providing at least one terpene lactam" in the context of the present disclosure means that at least one type of terpene lactam is provided. Accordingly, one or more different terpene lactams should be provided in step a).

The at least one terpene lactam provided in step a), that is to say the one or more different terpene lactams, is / are then in a step b), preferably with at least one non-terpene lactam or at least one bifunctional compound which has two amino groups at the end , has two carboxyl groups or one amino and one carboxyl group, polymerized with one another, preferably copolymerized.

With the present method and with the present manufactured products, a polyamide is surprisingly produced from renewable raw materials in a simple and inexpensive manner. The polyamides produced by the disclosed process or the disclosed or preferred polyamides are distinguished in particular by improved, in particular increased, transparency and / or higher strength. Alternatively or additionally, they are preferably also characterized by a higher toughness.

The polyamide is preferably prepared in that the at least one terpene lactam is preferably copolymerized with hexamethylene diamine adipate or other nylon salts, that is to say salts of, preferably longer-chain, diamines and dicarboxylic acids.

The polymerization of the at least one terpene lactam, preferably together with the at least one non-terpene lactam or the at least one bifunctional compound, requires that the at least one ring opening

CH 715 224 B1 a terpene lactam. The polymerization of the at least one terpene lactam, preferably with the further polymerizable components, results in step b) in a polyamide which contains the at least one ring-opened terpene lactam as a repeating unit.

In connection with the present invention, the term «terpene» is understood to mean a chemical compound which has one, two or more isoprene units. The terpenes are mono-, bi-, tri-, tetra- or pentacyclic. The group of terpenes includes monoterpenes (10 carbon atoms), sesquiterpenes (15 carbon atoms), diterpenes (20 carbon atoms), sesterterpenes (25 carbon atoms), triterpenes (30 carbon atoms) and tetraterpenes (40 carbon atoms). In the isoprene unit consisting of five carbon atoms, also referred to as C atoms, four carbon atoms are linearly linked to one another, with another carbon atom being covalently bonded at the C2 position, i.e. there is a branch at the C2 position. In connection with the present invention, the term “isoprene unit” is understood solely to mean the specific linkage of the five carbon atoms. The isoprene unit can therefore have no, one or two double bonds. The terpene preferably has a ring bridged with at least one carbon atom. In connection with the present invention, “terpenes” are also understood to mean derivatives of naturally occurring terpenes which have a double bond or on one or both carbon atoms adjacent to an alcohol group or a keto group by means of a conventional chemical reaction known from the prior art , preferably by means of an oxidation, reduction or addition reaction. For the preparation of a terpene derivative, therefore, at least one double bond in a naturally occurring terpene was preferably converted to an epoxide, diol, aldehyde or ketone. For the production of a terpene derivative, therefore, at least one halogen was preferably added to at least one double bond or at least one double bond was oxidized or epoxidized. Alternatively or additionally, the terpene derivative has been prepared by reacting a terpene ketone with an electrophile to form a keto group. The terpene derivative therefore has at least one, preferably exactly one, hydroxyl group, methyl group, benzyl group, ester group, o-NH-phenyl group or a halogen in the α-position to a keto group. The terpene derivative preferably has at least one, preferably exactly one, hydroxyl group, methyl group, benzyl group, ester group, o-NH-phenyl group or a halogen on one or both α-carbon atoms to the keto group. Alternatively or additionally, the terpene derivative has a hydroxyl group at the β-position to a keto group.

Alternatively or additionally, at least one halogen was preferably added α-permanently to an alcohol group or keto group of a terpene occurring in nature to produce a terpene derivative. As an alternative or in addition, at least one carbon which is α-position to a double bond was oxidized to an alcohol group or a keto group or a halogen was added to at least one carbon atom which is α-position to a double bond. The terpene derivative norbornene, also known as bicyclo [2.2.1] hept-2-ene, is preferred.

The terpene and / or the terpene lactam preferably has exactly (10 + Nx5) carbon atoms, with N preferably taking a value from 0 to 6.

In connection with the present disclosure, the term “polyamide” is understood to mean a compound which has monomer units, also referred to as repeating units, at least two of the repeating units being linked to one another via an amide bond. At least 10%, preferably at least 20%, preferably at least 30%, preferably at least 50%, preferably at least 70%, preferably at least 90%, preferably at least 99%, of all, preferably all, of the repeating units occurring in the polyamide are each linked via an amide compound , The term “polyamide” encompasses homopolymers and copolymers. In a preferred embodiment, the repeating units of the polyamide are linked to one another either via an amide bond or via an ester bond.

In connection with the present invention, the term “terpene lactam” is understood to mean a chemical compound which has at least one ring, also referred to as a cycle, the ring containing an amide bond -NH-CO-. The terpene lactam can preferably be produced from a terpene ketone, preferably by Beckmann rearrangement. Alternatively, the terpene lactam can preferably be produced from a terpene oxime by Beckmann rearrangement. The terpene oxime is preferably prepared by reacting a terpene ketone with a hydroxylamine or hydroxylamine derivative, the hydroxylamine derivative preferably being selected from hydroxylamine-O-sulfonic acid and hydroxylamine-O-acetate.

The terpene lactam can alternatively preferably be produced from a terpene having at least one double bond, the at least one, exactly one double bond of the terpene having at least one double bond being reacted with nitrosyl chloride (NOCI). In this reaction, a terpene oxime is first formed, which rearranges to the corresponding terpene lactam.

The terpene lactam can alternatively preferably be prepared from a terpene ketone, the terpene ketone being reacted with hydrochloric acid or azides and an acid, preferably a mineral acid, to give the corresponding lactam (Curtius reaction or Schmidt reaction).

The terpene lactam can alternatively preferably be prepared from a terpene ketone, the terpene ketone being reacted with hydroxylaminosulfonic acid or with hydroxylamine and hypochlorite. In this reaction, the keto group is first converted to an oxaziridine, the compound formed rearranging to the corresponding terpene lactam.

CH 715 224 B1 In connection with the present invention, the term “terpene ketone” is understood to mean a cyclic terpene with a keto group, the keto group being present in at least one ring, preferably exactly one ring, of the terpene ketone. The cyclic terpene preferably has a keto group on at least two rings, preferably on exactly two rings. In this preferred embodiment, the at least two, preferably exactly two, keto groups can each be converted to the lactam, so that the polymerization according to step b) and the ring opening of the at least two, preferably exactly two, rings result in branching in the polyamide to be produced. Accordingly, a terpene lactam with two lactam groups in two different rings of the terpene acts as a crosslinking component in the polyamide to be produced. The terpene ketone can either be present in nature in this form or it can be prepared from naturally occurring terpenes, which preferably have a double bond or a hydroxyl group. For example, the terpene ketone menthone can be produced by oxidation of the hydroxyl group of the menthol. The terpene ketone, preferably the a-pinene, can be prepared by converting a double bond present in a terpene, preferably the a-pinene, to the corresponding diol and then splitting off water. The terpene ketone, preferably the a-pinene, can alternatively preferably be prepared by directly converting a double bond present in a terpene, preferably the a-pinene, to a keto group.

The term “Beckmann rearrangement” is understood here to mean a rearrangement, a terpene lactam being produced from a terpene ketone using a hydroxylamine or a hydroxylamine derivative, preferably hydroxylamine-O-sulfonic acid or hydroxylamine-O-acetate. The Beckmann rearrangement has not been fully clarified mechanistically. According to a reaction mechanism recognized in the literature, the hydroxyl group of the ketoxime is first protonated. Water is split off there by migration of the transient carbon chain covalently bonded to the carbon atom of the ketoxime group to the nitrogen atom of the ketoxime group. Then water is attached to the positively charged carbon atom of the imine group and a proton is split off, so that the amide group is formed. The reaction of a terpene ketone with a hydroxylamine or a hydroxylamine derivative preferably results in two different terpene lactams.

In connection with the present disclosure, the term “activator component” is understood to mean a chemical compound which is provided for starting the activated, anionic polymerization according to step b). The activator component preferably serves as the starting point for the growth of a polyamide chain. The activator component is preferably a lactam having an electrophilic residue, and is preferably an N-acyl-lactam, preferably an N-acyl-s-caprolactam, an N-acyl-laurolactam, an N-acyl-terpene lactam or a mixture thereof. The activator component is preferably an N-acyl terpene lactam.

In connection with the present disclosure, the term “catalyst component” is understood to mean a chemical compound which enables the formation of lactamate anions, preferably terpene lactamate anions, and preferably catalyzes and preferably also starts the anionic polymerization. Deprotonated lactams, preferably deprotonated terpene lactams, are preferably used as the catalyst component, preferably in the form of a salt, also referred to as metal lactamate.

Both at least one catalyst component and at least one activator component are preferably used to activate a lactam, preferably the at least one terpene lactam, preferably in the anionic polymerization according to step b). Thus, a reactive system consisting of activator and catalyst component is preferably used.

The molar ratio of the at least one terpene lactam provided in step a) and the at least one catalyst component is particularly preferably at least 2: 1, preferably at least 10: 1, preferably at least 20: 1. The molar ratio between the at least one terpene lactam provided in step a) and the at least one catalyst component is preferably at most 100: 1, preferably at most 50: 1, preferably at most 10: 1. The molar ratio of the at least one terpene lactam provided in step a) and the at least one catalyst component is preferably 10,000: 1 to 10: 1, preferably 200: 1 to 20: 1.

[0028] The molar ratio of the at least one terpene lactam provided in step a) and the at least one activator component is particularly preferably at least 2: 1, preferably at least 10: 1, preferably at least 20: 1. The molar ratio between the at least one terpene lactam provided in step a) and the at least one activator component is preferably at most 100: 1, preferably at most 50: 1, preferably at most 10: 1. The molar ratio of the at least one terpene lactam provided in step a) and the at least one activator component is preferably 10,000: 1 to 10: 1, preferably 200: 1 to 20: 1.

A metal lactamate is preferably used as the catalyst component, the metal preferably being selected from the first three main groups of the periodic table. The metal lactamate is preferably a sodium lactamate or a magnesium lactamate. A metal lactamate is preferably used as the catalyst component, the lactamate being a terpene lactamate. The catalyst component is preferably dissolved in an anhydrous lactam. The concentration of the at least one catalyst component is preferably in a range from 0.01 to 10%, preferably 0.5 to 5% (based on the molar amount of the compounds to be polymerized).

The activator component is preferably an acylated lactam, an isocyanate blocked or a non-blocked isocyanate, a polyisocyanate or a derivative thereof, a carbodiimide, which is preferably also cyclic

CH 715 224 B1

Form can exist. Chemical compounds that can be used as the activator component are disclosed in Frunze et al., Russian Chemical Review, 1979, 48 (10), 991-1005.

The concentration of the at least one activator component is preferably in a range from 0.01 to 10%, preferably 0.1 to 10%, preferably 0.5 to 5% (based on the molar amount of the compounds to be polymerized).

Preferably, the catalyst component is present in a lactam present in the liquid state of aggregation during the polymerization or in a liquid, aprotic solvent.

At least two different terpene lactams are preferably provided in step a). Alternatively, exactly one terpene lactam, preferably exactly two different terpene lactams, is provided in step a). If at least two different terpene lactams are provided in step a), they are also copolymerized in step b). The at least two different monomers, where at least one of the two monomers is a terpene lactam, are preferably polymerized in step b) in such a way that random copolymers, block copolymers or a mixture thereof are formed. With “statistical copolymers”, the distribution of the at least two different monomers in the chain is random, that is, statistically distributed. In “block copolymers”, the polymer chain contains longer sequences or blocks of one monomer each.

In step a) at least one terpene lactam and at least one non-terpene lactam are preferably provided. Alternatively, at least one terpene lactam and at least one bifunctional compound are preferably provided in step a), the bifunctional compound being selected from a diamine, a dicarboxylic acid and an aminocarboxylic acid. The at least one bifunctional compound has two functional groups, namely the amino group and / or carboxylic acid group, the two functional groups preferably having an aromatic, non-aromatic, unsaturated or saturated carbon ring with preferably 3 to 20 carbon atoms, preferably 5 to 11 carbon atoms, or are connected to one another by a carbon chain with preferably 1 to 20 carbon atoms, preferably 3 to 11 carbon atoms, wherein at least one carbon atom, preferably at most half of the carbon atoms present in the carbon chain, has in each case been substituted by a hetero atom, the hetero atom has been independently selected from the group consisting of O, S, Se, NH, NR. The carbon ring and / or the carbon chain is / are preferably unsubstituted.

Preferably, the at least one non-terpene lactam ε-caprolactam and / or laurolactam.

[0036] In a preferred embodiment, chiral terpene lactams are provided in step a). A single diastereomer of the at least one terpene lactam is preferably provided alone in step a). The terpene lactam of (+) - camphor in step b) is preferably polymerized as the terpene lactam alone. Alternatively, the terpene lactam of (-) - camphor is preferably polymerized as the terpene lactam alone. Alternatively, the terpene lactam of (-) - camphor and (+) - camphor is polymerized as the preferred terpene lactam. The polyamide is preferably produced by first polymerizing alone (-) - camphor and independently polymerizing alone (+) - camphor and then copolymerizing the (-) - camphor polyamide with the (+) - camphor polyamide, whereby a copolymer, also known as a blend, is obtained. Alternatively, a mixture of (+) - camphor and (-) - camphor in step a) is preferably provided as terpene lactam and copolymerized in step b).

The terpene lactam provided in step a) is preferably obtained from a terpene oxime by Beckmann rearrangement. The terpene oxime is preferably made from a terpene ketone. Alternatively, the terpene lactam provided in step a) can preferably be obtained from a terpene ketone, the terpene oxime being formed in situ. The terpene ketone is preferably of natural origin. Alternatively, the terpene ketone is preferably obtained from terpenes which have an oxidizable double bond or secondary alcohol groups.

The polymerization, preferably copolymerization, of all the lactams and bifunctional compounds provided in step a) preferably takes place in step b).

The components provided in step a), in particular the at least one terpene lactam, are preferably melted before they are polymerized in step b). Alternatively, the components provided in step a), in particular the at least one terpene lactam, are preferably in liquid form. Alternatively, the at least one terpene lactam is preferably dissolved in a solvent, preferably in a non-terpene lactam or another terpene lactam.

In step b) there is preferably a copolymerization of the at least one terpene lactam and the at least one non-terpene lactam. The at least one terpene lactam and the at least one non-terpene lactam are preferably used in a ratio of 1:10 to 10: 1, preferably 5: 1 to 1: 5, preferably 1: 5 to 1:10, and copolymerized in step b) ,

A method is preferably provided, the polymerization in step b) being carried out anionically or hydrolytically. In anionic polymerization, an anion, preferably a deprotonated lactam, preferably deprotonated terpene lactam, preferably as a catalyst component and preferably in the form of a salt, also referred to as metal lactamate, is used.

Anionic polymerization is a type of polymerization customary in the prior art. It is within the technical knowledge to set process parameters and process conditions so that the information provided in step a) and in

CH 715 224 B1

Step b) components to be polymerized are successfully polymerized in step b) by means of anionic polymerization (see, for example, B. Tieke, Macromolecular Chemistry, Wiley VCH 2005).

In the hydrolytic polymerization, the ring opening of the terpene lactam is preferably carried out with the addition of catalytic, stoichiometric or superstoichiometric amounts of protic solvents. In the hydrolytic polymerization, the ring opening of the terpene lactam is preferably carried out with the addition of catalytic, stoichiometric or superstoichiometric amounts of water, an aqueous acid, an alcohol, ammonia or an amine. Through the addition of water, preferably supported by the protonation of the oxygen of the lactam group, the ring of the lactam opens. In a further process step, the terminal amino group of the ring-opened terpene lactam can attack the carbon atom of another lactam or a carboxylic acid or a derivative thereof.

The hydrolytic polymerization, also referred to as hydrolytic polycondensation, is preferably a discontinuous or continuous thermal hydrolytic polycondensation (see WO 2007/128 512 A2; plastics manual / polyamides, botten break / binsack). In the case of discontinuous or continuous thermal hydrolytic polycondensation, the polyamide is in one or more stages, preferably in exactly two stages, under pressure, preferably at 0.1 to 10 bar, preferably 0.5 to 5 bar, and a temperature, preferably of 100 up to 350 ° C, preferably 200 to 270 ° C.

The polyamide is preferably produced by activated, anionic polymerization, preferably in a RIM (Reaction in Mold) process for the production of cast polyamides, or by continuous reactive extrusion, preferably with the aid of extruders of different designs, for the production of thermoplastically processable polyamide ,

A method is preferably provided, wherein in step b) at least one catalyst component is added, which is preferably a deprotonated terpene lactam. In step b), at least one activator component is preferably used in addition to the at least one catalyst component, the at least one activator component being an N-acyl terpene lactam. Alternatively or additionally, the catalyst component can preferably be phosphoric acid, phosphorous acid or a derivative thereof.

A method is preferably provided, wherein the at least one terpene lactam is produced from a cyclic terpene ketone.

Preferably, the terpene ketone is converted to the terpene lactam by Beckmann rearrangement.

A method is preferably provided in which the cyclic terpene ketone is selected from the group consisting of the following structural formulas (I) or mixtures thereof:

CH 715 224 B1

A method is preferably provided, wherein the cyclic terpene ketone is selected from the structural formulas 1 to 12 and bicyclo [2.2.1] heptan-2-one.

A method is preferably provided, wherein the cyclic terpene ketone is selected from the group consisting of camphor, menthone, dihydrocarvone, carvone, isopiperitenone and those prepared from limonene, a-pinene, β-pinene, δ-pinene and 3-carene ketones.

The ketones prepared from limonene, a-pinene, δ-pinene and 3-carene are preferably formed from the terpenes limonene, a-pinene, δ-pinene and 3-carene by oxidation of the double bond present in these compounds to the ketone. Alternatively, the allylic carbon atom of a-pinene, β-pinene, δ-pinene or 3-carene is preferably oxidized to the ketone to produce the terpene ketone.

A method is preferably provided, wherein the terpene lactam is selected from the group consisting of the following structural formulas (II) or mixtures thereof:

CH 715 224 B1

CH 715 224 B1

The at least one terpene lactam is preferably selected from the structural formulas 13 to 36, 3Azabicyclo [3.2.1] octan-2-one and 2-Azabicyclo [3.2.1] octan-3-one.

A terpene lactam is preferably used as the only lactam in step b). The only terpene lactam is preferably a camphor lactam.

The polymerization according to step b) is preferably carried out at a temperature of at least 80 ° C., preferably at least 100 ° C., preferably at least 150 ° C., preferably at least 200 ° C., preferably 200 ° C. to 250 ° C. ,

The polyamide obtained in step c) preferably has a molecular weight M _n of 100 to 10,000,000 g / mol, preferably 200 to 4,000,000 g / mol, preferably 1000 to 1,000,000 g / mol, preferably 5000 to 100 000 g / mol (determined in each case

CH 715 224 B1 by gel permeation chromatography). The polyamide obtained in step c) preferably has at least 5, preferably at least 10, preferably at least 50, preferably at least 100, preferably at least 500, preferably at least 1000, monomeric repeating units of the compounds provided in step a), preferably of the at least one terpene lactam. The polyamide obtained in step c) preferably has a maximum of 5000, preferably a maximum of 2000, preferably a maximum of 1000, monomeric repeating units of the compounds provided in step a), preferably of the at least one terpene lactam.

The proportion of the at least one terpene lactam in the polyamide obtained in steps) is 0.01 to 100% by weight, preferably 1 to 100% by weight, preferably 20 to 100% by weight, preferably 20 to 80% by weight. %, preferably 30 to 70% by weight, preferably 40 to 60% by weight (in each case based on the total dry weight of the polyamide).

[0059] The disclosed method is preferably solvent-free.

In the hydrolytic polymerization, protic solvents, preferably alcohols or water, preferably water, are preferably used. The anionic polymerization is preferably carried out free of aprotic solvents, preferably free of any solvents.

The present disclosure relates to a polyamide which was produced by polymerizing at least one terpene lactam. The polyamide is preferably produced by the disclosed method.

The present disclosure also relates to a polyamide which has at least one terpene repeat unit X ¹ -LX ² , where X ¹ and X ² are selected independently of one another from the group consisting of an NH group and a C = O-- Group, wherein the at least one terpene repeat unit has at least one isoprene unit.

The terpene repeat unit preferably has X ¹ -LX ² , preferably additionally, (4 + n5) if X ¹ and X ^{2 are} not an NH group, or (5 + n5) if X ¹ and X ^{2 are} Are NH group, carbon atoms, where n has integer values from 0 to 7, preferably 1 to 3, preferably 1 to 2, preferably 1. The at least one terpene repeat unit X ¹ -LX ^{2 is} preferably a terpene repeat unit [-NH-L-CO-], [0064] The polyamide preferably has at least one first terpene repeat unit X ¹ -L ¹ -X ² and at least one a second terpene repeat unit X ¹ -L ² -X ² , where L ¹ is different from L ² .

[0065] The polyamide preferably has repeat terpene units alone as repeat units. The terpene repeat unit is preferably selected from the group consisting of [-NH-L-CO-], [-NH-L-NH-] and [-CO-L-CO-].

A polyamide is preferably provided, the at least one terpene repeat unit being selected from the group consisting of the following structural formulas (III) or mixtures thereof:

CH 715 224 B1

CH 715 224 B1

CH 715 224 B1

As an alternative or in addition, a polyamide is preferably provided, the at least one terpene repeat unit being selected from the group consisting of the following structural formulas (IV) or mixtures thereof:

CH 715 224 B1

CH 715 224 B1

78

CH 715 224 B1 The polyamide disclosed or produced according to the disclosed process preferably has at least one monomer of at least one ring-opened terpene lactam.

The polyamide disclosed or produced according to the disclosed process preferably has at least one monomer of at least one ring-opened terpene lactam, the at least one terpene lactam from the structural formulas 13 to 36, 3-azabicyclo [3.2.1] octan-2-one and 2 -Azabicyclo [3.2.1] octan-3-one is selected.

The at least one terpene lactam is preferably prepared from a cyclic terpene with a keto group, an alcohol group or a double bond, the terpene preferably having a bridged ring.

Preferably, the polyamide disclosed or prepared according to the disclosed process has 1 to 100%, preferably 5 to 100%, of the at least one ring-opened terpene lactam (based on all repeating units present in the polyamide).

Preferably, the polyamide disclosed or produced according to the disclosed process has a polydispersity D, also referred to as polydispersity Q, of less than 10, preferably less than 5.

Preferably, the polyamide disclosed or produced according to the disclosed process has a relative viscosity η _Γ θι of> 1.5, preferably from> 1.5 to 7, preferably> 1.5 to 5 (measured in a 1- % By weight solution in 96% sulfuric acid analogous to DIN EN ISO 307).

In addition to the at least one ring-opened terpene lactam, the polyamide disclosed or produced according to the disclosed process has at least one further ring-opened lactam, preferably a ring-opened non-terpene lactam, the lactam, preferably the non-terpene lactam, having 4 to 12 carbon atoms.

The polyamide is preferably obtained in the form of a compact solid, a granulate, a powder, a fiber, a plate, a tube, a jacket, a shaped or profiled piece or the like.

The technical problem of the present invention is solved by providing a method for producing at least one terpendiamine, the method comprising the following steps:

I) providing at least one terpene lactam,

II) ring-opening reaction of the at least one terpene lactam provided in step I), so that at least one ring-opened terpene lactam with amino and carboxyl group is obtained, ili) reaction of the carboxyl group of the at least one ring-opened terpene lactam with amino and carboxyl group to form an aldehyde group, so that at least a ring-opened terpene lactam with amino and aldehyde group is obtained, iv) reacting the aldehyde group of the at least one ring-opened terpene lactam with amino and aldehyde group into an amino group, so that at least one terpendiamine is obtained, and

v) obtaining the at least one terpendiamine.

In step ili), the carboxyl group is preferably first reduced to a hydroxyl group and the hydroxyl group obtained is then selectively oxidized to the aldehyde group.

The reaction of the aldehyde group in step iv) is preferably carried out by reductive amination or by adding hydroxylamine and then reducing the oxime group formed.

[0079] The technical problem of the present invention is solved by providing a method for producing at least one terpendiamine, the method comprising the following steps:

aa) providing at least one terpene lactam, bb) reacting the at least one terpene lactam provided in step aa) with ammonia, so that a ring-opened terpene lactam with amino and nitrile group is obtained, cc) reducing the nitrile group of the at least one ring-opened terpene lactam with amino and nitrile group an amino group so that at least one terpendiamine is obtained, and dd) obtaining the at least one terpendiamine.

The terpendiamine obtained in step iv) or cc) is preferably selected from the group consisting of the following structural formulas (V) or mixtures thereof:

CH 715 224 B1

CH 715 224 B1

CH 715 224 B1 The use of at least one deprotonated terpene lactam, preferably in the form of a metal terpene lactamate, as a catalyst component in the production of a polyamide is also disclosed. In addition to using the at least one deprotonated terpene lactam, at least one N-acyl terpene lactam is used as the activator component in the production of a polyamide.

The N-acyl terpene lactam can preferably be prepared by acylating the lactam nitrogen of a terpene lactam.

Terpene lactams are preferably the terpene lactams disclosed above, preferably with the structural formulas (I).

In a preferred embodiment, all statements made mutatis mutandis in connection with the disclosed or preferred method and / or the disclosed or preferred polyamide also apply to the inventive method for the production of a terpendiamine and / or the disclosed use of a deprotonated terpene lactam and / or of an N-acyl terpene lactam.

The present disclosure also relates to a metal terpene lactamate. The metal of the metal terpene lactamate is preferably selected from the first three main groups of the periodic table. Preferably the metal terpene lactamate is a sodium terpene lactamate or a magnesium terpene lactamate.

Preferred embodiments of the present invention result from the subclaims.

In all of the above structural formulas 1 to 108, no concrete statement is made about the stereochemistry of the stereochemical, preferably chiral, centers in the individual compounds. If one or more stereochemical, preferably chiral, centers are / are present in structural formulas 1 to 108, then all variants of a possible spatial arrangement of the residues are included.

Example (not according to the invention):

Production of a copolymer of ε-caprolactam and the lactam synthesized from camphor.

36.2 g of ε-caprolactam (Merck), 10.0 g of the lactam produced from camphor, also known as camphor lactam, are in a 250 ml 2-necked flask with magnetic stirrer, reflux condenser and dropping funnel with exclusion of air and moisture , and 0.361 g of acyl caprolactam (activator: Brüggemann C20P) and heated to 200 ° C to melt.

In a dropping funnel with exclusion of air and moisture a heated to 80 ° C-100 ° C and thus melted mixture of 9.47 g ε-caprolactam and 3.36 g sodium lactamate (Brüggemann 010) is presented and in large portions Melt added in the round bottom flask. The reaction mixture is kept at 210 ° C. for 25 minutes, during which it solidifies.

After cooling, the reaction vessel is destroyed and the product thus obtained is mechanically comminuted.

To determine the unreacted residual monomers, 3.15 g of polymer comminuted to powder with about 10% residual moisture in 43 ml of deionized water are heated to reflux for 24 hours. The suspension is filtered hot, the solid is dried and the thermal properties are determined by dynamic differential calorimetry (DSG). 2.16 g of solid are obtained. The solvent in the mother liquor is removed in vacuo and the residue is also dried. 0.660 g are obtained. Gas chromatographic mass spectrometric (GC-MS) analysis of this extracted material shows a ratio of ε-caprolactam to camphor-based lactam of 1: 9.

Claims (5)

claims 1. A process for the preparation of a terpendiamine, the process comprising the following steps: I) providing at least one terpene lactam, II) ring-opening reaction of the at least one terpene lactam provided in step I), so that at least one ring-opened terpene lactam with amino and carboxyl group is obtained, ili) reaction of the carboxyl group of the at least one ring-opened terpene lactam with amino and carboxyl group to an aldehyde group, so that at least one ring-opened Terpene lactam with amino and aldehyde group is obtained, iv) reacting the aldehyde group of the at least one ring-opened terpene lactam with amino and aldehyde group to an amino group, so that at least one terpendiamine is obtained. 2. The method according to claim 1, wherein in step ili) the carboxyl group is first reduced to a hydroxyl group and the hydroxyl group obtained is then selectively oxidized to the aldehyde group. 3. The method according to claim 1 or 2, wherein the reaction of the aldehyde group in step iv) by reductive amination or by adding hydroxylamine and then reducing the resulting oxime group. 4. A process for the preparation of a terpendiamine, the process comprising the following steps: aa) providing at least one terpene lactam, CH 715 224 B1 bb) reacting the at least one terpene lactam provided in step aa) with ammonia, so that a ring-opened terpene lactam with amino and nitrile group is obtained, cc) reducing the nitrile group of the at least one ring-opened terpene lactam with amino and nitrile group to an amino group, so that at least one terpendiamine is obtained. 5. The method according to any one of the preceding claims, wherein the at least one terpendiamine obtained in step iv) or cc) is selected from the group consisting of the following structural form (V) or mixtures thereof:

CH 715 224 B1

106

107

nh ₂ 108