DE102014221061B4 - Terpene lactam based polyamides - Google Patents

Abstract

A method of making a polyamide, the method comprising the steps of: a) providing at least one terpene lactam, b) polymerizing the at least one terpene lactam ring opening to give a polyamide; and c) obtaining the polyamide containing at least one ring-opened terpene lactam, said polymerizing according to step b), anionically in the presence of at least one lactam having an electrophilic radical as activator component and at least one deprotonated lactam as catalyst component, the polyamide obtained in step c) comprising at least 10 monomeric repeating units of at least one terpene lactam provided in step a) and the at least a terpene lactam is selected from the group consisting of the following structural formulas (II) or mixtures thereof:

Description

The present invention relates to a process for producing a polyamide, a polyamide thus prepared, a polyamide having a terpene repeating unit X ¹ -LX ^2, and a process for producing a terpene diamine.

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 with dicarboxylic acids and amino acids with amino acids can be reacted. In the case of the latter, the amino group and the carboxyl group have both functional groups required for linking in the same molecule. Among others, lactams, such as ε-caprolactam, can be used by ring-opening polymerization for the preparation of polyamides. Two industrially important lactams which are used for ring-opening polymerization are ε-caprolactam for the preparation of polyamide-6 and laurolactam for the preparation of polyamide-12.

ε-Caprolactam is industrially produced from cyclohexanone and laurolactam from cyclododecanone. In this case, the ketone is first converted to the oxime and this oxime then by a Beckmann rearrangement to lactam. Alternatively, the ketone is converted to the lactam in a single reaction, with oxime formation occurring in situ.

Lactams of camphor and menthone have been described in the literature ( Kumar, Med. Chem. Res. 2012, page 531 ). The lactams from α-pinene and 3-carene are known from the literature ( RE Gawley, Org. React. 1988, 35, 1 ). Lochinski et al. (Tetrahedron: Asymmetry, 2000, 11, 1295) discloses the 3-carene lactam and the ring-opened aminocarboxylic acid prepared therefrom. Winnacker et al. (Macromol Chem. Phys., 2014, 215, pages 1654-1660) describes the synthesis of oligoamides by ring-opening polymerization of (-) - menthone-based lactams.

There is a need in the art for starting materials for the production of polyamides from renewable resources.

It is therefore an object of the present invention to provide a process for the preparation of polyamides, renewable raw materials being used as starting compounds.

In particular, the polyamide produced thereby 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 renewable raw materials based polyamides 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.

The object of the present invention is achieved in particular by the teaching of the independent claims.

• a) Bereitstellen mindestens eines Terpenlactams,
• b) Polymerisieren des mindestens einen Terpenlactams unter Ringöffnung, sodass ein Polyamid, bevorzugt ein Homopolyamid oder ein Copolyamid, erhalten wird und
• c) Erhalten des Polyamids, bevorzugt des Homopolyamids oder des Copolyamids, enthaltend mindestens ein ringgeöffnetes Terpenlactam,

wobei das Polymerisieren gemäß Schritt b) anionisch in Anwesenheit mindestens eines einen elektrophilen Rest aufweisenden Lactams als Aktivatorkomponente und mindestens eines deprotonierten Lactams als Katalysatorkomponente erfolgt, wobei das in Schritt c) erhaltene Polyamid mindestens 10 monomere Wiederholungseinheiten des in Schritt a) bereitgestellten mindestens einen Terpenlactams umfasst und das mindestens eine Terpenlactam ausgewählt ist aus der Gruppe bestehend aus den nachfolgenden Strukturformeln (II) oder Gemischen davon:

In particular, there is provided a process for producing a polyamide, the process comprising the steps of:

• 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,

wherein the polymerizing according to step b) is carried out anionically in the presence of at least one lactam having an electrophilic radical as activator component and at least one deprotonated lactam as catalyst component, wherein the polyamide obtained in step c) comprises at least 10 monomeric repeating units of the at least one terpene lactam provided in step a) and that at least a terpene lactam is selected from the group consisting of the following structural formulas (II) or mixtures thereof:

In particular, therefore, the object is achieved by a process for producing a polyamide, wherein in a step a) at least one terpene lactam is provided. The expression "providing at least one terpene lactam" in connection with the present invention means that at least one terpene lactam species is provided. Accordingly, in step a) one or more different terpene lactams should be provided.

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

Surprisingly, a polyamide is produced from renewable raw materials in a simple and cost-effective manner with the present process and with the products produced here. The polyamides produced by the process according to the invention or preferred according to the invention or the polyamides according to the invention or preferred according to the invention are distinguished in particular by an 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 by copolymerizing the at least one terpene lactam preferably with hexamethylene diamine adipate or other nylon salts, that is, 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 ring opening of the at least one terpene lactam takes place. By the polymerization of the at least one terpene lactam, preferably with the other polymerisable components, a polyamide is produced in step b) which contains as repeat unit the at least one ring-opened terpene lactam.

In the context of 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), ester terpenes (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 carbon atoms, four carbon atoms are linearly linked to one another, wherein another carbon atom is covalently bonded at the C2 position, ie a branching is present at the C2 position. In the context of the present invention, the term "isoprene unit" alone means the specific linking of the five carbon atoms. The isoprene unit can therefore have none, one or two double bonds. The terpene preferably has a ring bridged with at least one carbon atom. In the context of the present invention, "terpenes" are also understood to mean derivatives of naturally occurring terpenes which are bonded to a double bond or to one or both of the carbon atoms adjacent to an alcohol group or a keto group by means of a chemical reaction known and customary in the prior art , preferably by means of an oxidation, reduction or addition reaction, are modified. For the preparation of a terpene derivative, preference has therefore been given to reacting at least one double bond in a naturally occurring terpene to form an epoxide, diol, aldehyde or ketone. For the preparation of a terpene derivative, preference has therefore been given to attaching at least one halogen to at least one double bond or oxidizing or epoxidizing at least one double bond. Alternatively or additionally preferred is the terpene derivative through to a keto group α-permanent reaction of a terpene ketone with an electrophile been prepared. The terpene derivative therefore has in α-position to a keto group at least one, preferably exactly one, hydroxyl group, methyl group, benzyl group, ester group, o-NH-phenyl group or a halogen. Preferably, the terpene derivative 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 preferably, the terpene derivative has a hydroxyl group β-permanently to a keto group. Alternatively or additionally, to produce a terpene derivative, it has been preferred to add α-permanently to an alcohol group or keto group of a terpene occurring in nature, at least one halogen. Alternatively or additionally, at least one carbon which is α-terminal to a double bond has been oxidized to an alcohol group or a keto group, or at least one halogen has been added to at least one α-carbon atom to a double bond. Preferably, the terpene derivative norbornene, also referred to as bicyclo [2.2.1] hept-2-ene.

Preferably, the terpene and / or the terpene lactam has exactly (10 + Nx5) carbon atoms, wherein N preferably assumes a value of 0 to 6.

In the context of the present invention, the term "polyamide" means a compound which comprises monomer units, also referred to as repeat units, wherein at least two of the repeat units are linked to one another via an amide bond. Preferably 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%, all, preferably all repeating units occurring in the polyamide in each case via an amide compound with each other connected. The term "polyamide" includes homopolymers as well as copolymers. In a preferred embodiment, the repeating units of the polyamide are linked together either via an amide bond or via an ester linkage.

In the context of 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, wherein the ring contains an amide bond -NH-CO-. The terpene lactam may preferably be prepared from a terpene ketone, preferably by Beckmann rearrangement. Alternatively, the terpene lactam may preferably be prepared from a terpenoxime by Beckmann rearrangement. The terpenoxime is preferably prepared by reacting a terpene ketone with a hydroxylamine or hydroxylamine derivative, wherein the hydroxylamine derivative is preferably selected from hydroxylamine-O-sulfonic acid and hydroxylamine-O-acetate.

Alternatively, the terpene lactam may preferably be prepared from a terpene having at least one double bond, the at least one terpene having exactly one double bond of the at least one double bond being reacted with nitrosyl chloride (NOC1). In this reaction, a terpenoxime is initially formed which rearranges to the corresponding terpene lactam.

Alternatively, the terpene lactam may preferably be prepared from a terpene ketone wherein the terpene ketone is reacted with hydrazoic acid or azides and an acid, preferably a mineral acid, to form the corresponding lactam (Curtius reaction or Schmidt reaction).

Alternatively, the terpene lactam may preferably be prepared from a terpene ketone wherein the terpene ketone is reacted with hydroxylaminosulfonic acid or with hydroxylamine and hypochlorite. In this reaction, the keto group is first converted to an oxaziridine, wherein the resulting compound rearranges to the corresponding terpene lactam.

In the context of the present invention, the term "terpene ketone" is understood to mean a cyclic terpene having a keto group, where the keto group is 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 a branching in the polyamide to be produced results from the polymerization in step b) and the ring opening of the at least two rings, preferably exactly two rings. Accordingly, a terpene lactam having two lactam groups in two different rings of 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 prepared by oxidation of the hydroxyl group of the menthol. The terpene ketone, preferably of the α-pinene, can be prepared by reacting a double bond present in a terpene, preferably the α-pinene, to the corresponding diol and subsequent dehydration can be produced. Alternatively, the terpene ketone, preferably the α-pinene, may be prepared by directly reacting a double bond present in a terpene, preferably the α-pinene, to a keto group.

The term "Beckmann rearrangement" is understood here to mean a rearrangement, a terpene ketone being prepared from a terpene ketone using a hydroxylamine or a hydroxylamine derivative, preferably hydroxylamine-O-sulfonic acid or hydroxylamine O-acetate. The Beckmann rearrangement is mechanistically not fully understood. According to a reaction mechanism recognized in the literature, the hydroxyl group of the ketoxime is first protonated. Migration of the trans-acting carbon chain covalently bonded to the carbon atom of the ketoxime group to the nitrogen atom of the ketoxime group causes water to split off there. Subsequently, water is deposited on the positively charged carbon atom of the resulting imine group and a proton is split off to form the amide group. By reacting a terpene ketone with a hydroxylamine or a hydroxylamine derivative, preferably two different terpene lactams are formed.

In the context of the present invention, the term "activator component" is understood as meaning a chemical compound which is provided for initiating the activated anionic polymerization according to step b). The activator component preferably serves as a starting point for the growth of a polyamide chain. The activator component according to the present invention is an electrophilic residue-having lactam, and is preferably an N-acyl lactam, preferably an N-acyl-ε-caprolactam, an N-acyl-laurolactam, an N-acyl-terpene lactam, or a mixture from that. Preferably, the activator component is an N-acyl terpene lactam.

In the context of the present invention, the term "catalyst component" means a chemical compound which allows the formation of lactamate anions, preferably of terpene lactamate anions, and preferably catalyzes and preferably also starts the anionic polymerization. The catalyst component used according to the present invention deprotonated lactams, preferably deprotonated terpene lactams, preferably in the form of a salt, also referred to as metal lactamate.

According to the invention, both at least one catalyst component and at least one activator component for activating a lactam, preferably the at least one terpene lactam, are used in the anionic polymerization according to step b). Thus, according to the invention a reactive system consisting of activator and catalyst component is 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 Step a) provided terpene lactam and the at least one catalyst component at a maximum of 100: 1, preferably at a maximum of 50: 1, preferably at a maximum of 10: 1. Preferably, the molar ratio of the at least one provided in step a) terpene lactam and the at least one catalyst component at 10,000: 1 to 10: 1, preferably 200: 1 to 20: 1.

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 Step a) provided terpene lactam and the at least one activator component at a maximum of 100: 1, preferably at a maximum of 50: 1, preferably at a maximum of 10: 1. Preferably, the molar ratio of the at least one provided in step a) terpene lactam and the at least one activator component at 10,000: 1 to 10: 1, preferably 200: 1 to 20: 1.

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

Preferably, the activator component is an acylated lactam, a blocked or unblocked isocyanate, a polyisocyanate or a derivative thereof, a carbodiimide which preferably can also be present in cyclic form. Chemical compounds that can be used as the activator component are in Frunze et al., Russian Chemical Review, 1979, 48 (10), 991-1005 disclosed.

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

The catalyst component is preferably present in a lactam present in the state of liquid aggregation during the polymerization carried out according to the invention or dissolved in a liquid, aprotic solvent.

Preferably, at least two different terpene lactams are provided in step a). Alternatively, in step a), exactly one terpene lactam, preferably exactly two different terpene lactams, is provided. 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, wherein 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. In the case of "random copolymers", the distribution of the at least two different monomers in the chain is random, ie statistically distributed. In "block copolymers", the polymer chain contains longer sequences or blocks of one monomer each.

At least one terpene lactam and at least one non-terpene lactam are preferably provided in step a). Alternatively, preferably in step a) at least one terpene lactam and at least one bifunctional compound are provided, wherein the bifunctional compound is selected from a diamine, a dicarboxylic acid and an amino carboxylic acid. The at least one bifunctional compound has two functional groups, namely the amino group and / or carboxylic acid group, terminal, wherein the two functional groups preferably by an aromatic, non-aromatic, unsaturated or saturated carbon ring having preferably three to 20 carbon atoms, preferably 5 to 11 carbon atoms, or by a carbon chain having preferably 1 to 20 carbon atoms, preferably 3 to 11 carbon atoms, wherein optionally at least one carbon atom, preferably at most half of the carbon atoms present in the carbon chain, has been substituted by one heteroatom each, said heteroatom being independent has been 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 is ε-caprolactam and / or laurolactam.

In a preferred embodiment, chiral terpene lactams are provided in step a). Preferably, only a single diastereomer of the at least one terpene lactam is provided in step a). Preferably, as terpene lactam alone, the terpene lactam is polymerized by (+) - camphor in step b). Alternatively, as terpene lactam alone, the terpene lactam is polymerized by (-) - camphor. Alternatively, as terpene lactam alone, the terpene lactam is polymerized by (-) - camphor and (+) - camphor. Preferably, the polyamide is prepared by first polymerizing (-) - camphor alone and polymerizing independently (+) - camphor and then copolymerizing the (-) - camphor polyamide with the (+) - camphor polyamide, whereby a mixed polymer, also referred to as blend, is obtained. Alternatively, a mixture of (+) - camphor and (-) - camphor in step a) is provided as terpene lactam and copolymerized in step b).

The terpene lactam provided in step a) is preferably obtained by Beckmann rearrangement from a terpenoxime. The terpenoxime is preferably prepared from a terpene ketone. Alternatively, the terpene lactam provided in step a) may preferably be obtained from a terpene ketone, wherein the formation of terpenoxime occurs in situ. The terpene ketone is preferably of natural origin. Alternatively, preferably, the terpene ketone is derived from terpenes having an oxidizable double bond or secondary alcohol groups.

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

Preference is given to melting the components provided in step a), in particular the at least one terpene lactam, before they are polymerized in step b). Alternatively preferred are the components provided in step a), in particular the at least one terpene lactam in liquid form in front. Alternatively, preferably, the at least one terpene lactam is dissolved in a solvent, preferably in a non-terpene lactam or other terpene lactam.

In step b), preference is given to copolymerizing 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).

In accordance with the present disclosure, a process is provided wherein the polymerization in step b) is anionic or hydrolytic. In the case of the anionic polymerization according to the invention, an anion, preferably a deprotonated lactam, preferably deprotonated terpene lactam, is preferably used as the catalyst component and preferably in the form of a salt, also referred to as metal lactamate.

Anionic polymerization is a conventional type of polymerization in the art. It is within the skill of the art to adjust process parameters and process conditions so that the components provided in step a) and to be polymerized in step b) are successfully polymerized in step b) by means of an anionic polymerization (see 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. By the addition of water, preferably supported by the protonation of the oxygen of the lactam group, the ring of lactam opens. The terminal amino group of the ring-opened terpene lactam may, in a further process step, 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 2007/128512 A2 ; Kunststoffhandbuch / Polyamide, Bottenbruch / 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 to 350 ° C, preferably 200 to 270 ° C, prepared.

According to the invention, the polyamide is produced by activated, anionic polymerization, preferably in a RIM (Reaction in Mold) process for the production of cast polyamides, or by a continuous reactive extrusion, preferably by means of extruders of various designs, for the production of thermoplastically processable polyamide.

According to the invention, a process is 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, wherein the at least one activator component is an N-acyl terpene lactam. The catalyst component may alternatively or additionally preferably be phosphoric acid, phosphorous acid or a derivative thereof.

Preferably, a method is provided, wherein the at least one terpene lactam is prepared from a cyclic terpene ketone.

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

According to the present disclosure, a method is preferably provided, wherein the cyclic terpene ketone is selected from the group consisting of the following structural formulas (I) or mixtures thereof:

According to the present invention, a method is preferably provided, wherein the cyclic terpene ketone is selected from the group consisting of the following structural formulas (I) or mixtures thereof:

According to the present disclosure, 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.

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

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

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

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

According to the present disclosure, in step b), a terpene lactam is preferably used as sole lactam. Preferably, the only terpene lactam is a camphor lactam.

The polymerization according to step b) is preferably carried out at a temperature of at least 80 ° C., preferably of at least 100 ° C., preferably of at least 150 ° C., preferably of 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 1,000 to 1,000,000 g / mol, preferably 5,000 to 100,000 g / mol (in each case determined by gel permeation chromatography). According to the present disclosure, the polyamide obtained in step c) preferably has at least five, preferably at least 10, preferably at least 50, preferably at least 100, preferably at least 500, preferably at least 1000, monomeric repeat units of the compounds provided in step a), preferably the at least one Terpene lactams, up. According to the invention, the polyamide obtained in step c) has at least 10 monomeric repeating units of the at least one terpene lactam provided in step a). The polyamide obtained in step c) preferably has a maximum of 5000, preferably a maximum of 2000, preferably a maximum of 1000, monomeric repeat 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 step c) is from 0.01 to 100% by weight, preferably from 1 to 100% by weight, preferably from 20 to 100% by weight, preferably from 20 to 80% by weight. %, preferably 30 to 70 wt .-%, preferably 40 to 60 wt .-% (each based on the total dry weight of the polyamide).

The process according to the invention or preferred according to the invention is preferably solvent-free.

Protic solvents, preferably alcohols or water, preferably water, are preferably used in the hydrolytic polymerization. The anionic polymerization is preferably carried out free from aprotic solvents, preferably free from any solvents.

In particular, the object of the present invention is achieved by a polyamide prepared by polymerizing at least one terpene lactam. According to the invention, the polyamide is produced by a process according to the invention or preferred according to the invention.

In particular, the object of the present invention is achieved by a polyamide which has at least one terpene repeating unit X ¹ -LX ² , where X ¹ and X ^{2 are} independently selected from the group consisting of an NH group and a C = O- Group, wherein the at least one terpene repeating unit has at least one isoprene unit.

Preferably, the terpene repeating unit X ¹ -LX ² , preferably in addition, (4 + n5), if X ¹ and X ^{2 are} not NH group, or (5 + n5), if X ¹ and X ^{2 is} an NH group are carbon atoms, where n has integer values of 0 to 7, preferably 1 to 3, preferably 1 to 2, preferably of 1. Preferably, the at least one terpene repeating unit X ¹ -LX ^{2 is} a terpene repeating unit [-NH-L-CO-].

The polyamide preferably has at least one first terpene repeat unit X ¹ -L ¹ -X ² and at least one second terpene repeat unit X ¹ -L ² -X ² , where L ¹ is different from L ² .

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

According to the present disclosure, a polyamide is preferably provided, wherein the at least one terpene repeating unit is selected from the group consisting of the following structural formulas (III) or mixtures thereof:

According to the invention, a polyamide is preferably provided, wherein the at least one terpene repeating unit is selected from the group consisting of the following structural formulas (III) or mixtures thereof:

According to the present disclosure, a polyamide is preferably provided alternatively or additionally, wherein the at least one terpene repeating unit is selected from the group consisting of the following structural formulas (IV) or mixtures thereof:

According to the invention, alternatively or additionally, a polyamide is provided, wherein the at least one terpene repeating unit is selected from the group consisting of the following structural formulas (IV) or mixtures thereof:

The polyamide according to the invention or prepared according to the invention preferably has at least one monomer of at least one ring-opened terpene lactam.

According to the present disclosure, the polyamide according to the invention or produced according to the invention preferably comprises at least one monomer of at least one ring-opened terpene lactam, wherein 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 having a keto group, an alcohol group or a double bond, the terpene preferably having a bridged ring.

The polyamide according to the invention or produced according to the invention preferably has from 1 to 100%, preferably from 5 to 100%, of the at least one ring-opened terpene lactam (based on all repeating units present in the polyamide).

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

The polyamide according to the invention or prepared according to the invention preferably has a relative viscosity η _rel of> 1.5, preferably of> 1.5 to 7, preferably> 1.5 to 5 (measured in a 1% strength by weight solution in 96% sulfuric acid analogous to DIN EN ISO 307 ).

The polyamide according to the invention or prepared according to the invention has in addition to the at least one ring-opened terpene lactam at least one further ring-opened lactam, preferably a ring-opened non-terpene lactam, wherein the lactam, preferably the non-terpene lactam, has 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 sheath, a shaped or profiled piece or the like.

• i) Bereitstellen mindestens eines Terpenlactams,
• ii) ringöffnende Umsetzung des in Schritt i) bereitgestellten mindestens einen Terpenlactams, sodass mindestens ein ringgeöffnetes Terpenlactam mit Amino- und Carboxylgruppe erhalten wird,
• iii) Umsetzen der Carboxylgruppe des mindestens einen ringgeöffneten Terpenlactams mit Amino- und Carboxylgruppe zu einer Aldehyd-Gruppe, sodass mindestens ein ringgeöffnetes Terpenlactam mit Amino- und Aldehydgruppe erhalten wird,
• iv) Umsetzen der Aldehyd-Gruppe des mindestens einen ringgeöffneten Terpenlactams mit Amino- und Aldehydgruppe zu einer Aminogruppe, sodass mindestens ein Terpendiamin erhalten wird und
• v) Erhalten des mindestens einen Terpendiamins.

In particular, the technical problem of the present invention is solved by providing a process for producing at least one terpene diamine, 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 having an amino and carboxyl group is obtained,
• iii) reacting the carboxyl group of the at least one ring-opened terpene lactam having amino and carboxyl group to form 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 form an amino group, so that at least one terpene diamine is obtained and
• v) obtaining the at least one terpene diamine.

Preferably, in step iii), the carboxyl group is first reduced to a hydroxyl group, and then the resulting hydroxyl group is selectively oxidized to the aldehyde group.

The reaction of the aldehyde group in step iv) is preferably carried out by reductive amination or by addition of hydroxylamine and subsequent reduction of the resulting oxime group.

• aa) Bereitstellen mindestens eines Terpenlactams,
• bb) Umsetzen des in Schritt aa) bereitgestellten mindestens einen Terpenlactams mit Ammoniak, sodass ein ringgeöffnetes Terpenlactam mit Amino- und Nitrilgruppe erhalten wird,
• cc) Reduzieren der Nitrilgruppe des mindestens einen ringgeöffneten Terpenlactams mit Amino- und Nitrilgruppe zu einer Aminogruppe, sodass mindestens ein Terpendiamin erhalten wird und
• dd) Erhalten des mindestens einen Terpendiamins.

In particular, the technical problem of the present invention is solved by providing a process for producing at least one terpene diamine, the process 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 having an amino and nitrile group is obtained,
• cc) reducing the nitrile group of the at least one ring-opened terpene lactam having amino and nitrile group to an amino group, so that at least one terpene diamine is obtained and
• dd) obtaining the at least one terpene diamine.

According to the present disclosure, the terpene diamine obtained in step iv) or cc) is preferably selected from the group consisting of the following structural formulas (V) or mixtures thereof:

According to the present invention, the terpene diamine obtained in step iv) or cc) is preferably selected from the group consisting of the following structural formulas (V) or mixtures thereof:

The present disclosure further relates to the use of at least one deprotonated terpene lactam, preferably in the form of a metal terpene lactamate, as a catalyst component in the preparation of a polyamide. 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 preparation of a polyamide.

The N-acyl terpene lactam may preferably be prepared by acylation of the lactam nitrogen of a terpene lactam.

Terpene lactams are preferably understood to mean the above terpene lactams according to the invention, preferably having the structural formulas (I).

In a preferred embodiment, all methods and / or the preferred or preferred polyamide according to the invention or the present invention are mutatis mutandis also applicable to the process for preparing a terpene diamine and / or the use of a deprotonated terpene lactam and / or an N-acyl group. Terpenlactams.

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 will become apparent from the dependent claims.

The present invention will be explained in more detail with reference to the following example.

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

Example:

Preparation of a copolymer of ε-caprotactam and camphor-synthesized lactam.

In a 250 ml 2-necked flask equipped with magnetic stirrer, reflux condenser and dropping funnel, 36.2 g of ε-caprolactam (Merck), 10.0 g of camphor-derived lactam, also referred to as camphor lactam, and 0.361 g are added with exclusion of air and moisture Acyl-caprolactam (activator: Brüggemann C20P) submitted and brought by heating to 200 ° C to melt.

In a dropping funnel, a mixture of 9.47 g of ε-caprolactam and 3.36 g of sodium lactamate (Brüggemann C10) heated to 80 ° C.-100 ° C. is placed under exclusion of air and moisture and added in large portions to the melt in the round bottom flask added. The reaction mixture is held for 25 minutes at 210 ° C, where it solidifies.

After cooling, the reaction vessel is destroyed and the product thus obtained 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 dried and the thermal properties determined by differential scanning calorimetry (DSC). There are obtained 2.16 g of solid. The solvent of the mother liquor is removed in vacuo and the residue is also dried. There are obtained 0.660 g. Gas chromatographic mass spectroscopic (GC-MS) analysis of this extracted material shows a ratio of ε-caprolactam to camphor-based lactam of 1: 9.

Claims (10)

A process for producing a polyamide, the process comprising the steps of: a) providing at least one terpene lactam, b) polymerizing the at least one terpene lactam with ring opening to give a polyamide, and c) obtaining the polyamide containing at least one ring-opened terpene lactam; Polymerizing according to step b) anionically in the presence of at least one electrophilic radical having lactam as activator component and at least one deprotonated lactam as catalyst component, wherein the polyamide obtained in step c) comprises at least 10 monomeric repeating units of provided in step a) at least one terpene lactam and the at least one terpene lactam is selected from the group consisting of the following structural formulas (II) or mixtures thereof:

A process according to any one of the preceding claims, wherein the at least one terpene lactam is prepared from a cyclic terpene ketone. Method according to Claim 2 wherein the cyclic terpene ketone is selected from the group consisting of the following structural formulas (I):

Polyamide prepared by the method according to any one of Claims 1 to 3 , Polyamide after Claim 4 , characterized in that the polyamide has at least one terpene repeating unit X ¹ -LX ² , wherein X ¹ and X ^{2 are} independently selected from the group consisting of an NH group and a C = O group and wherein the at least one Terpen repeat unit has at least one isoprene unit. Polyamide after Claim 5 wherein the at least one terpene repeating unit is selected from the group consisting of the following structural formulas (III) or mixtures thereof:

Polyamide after Claim 5 wherein the at least one terpene repeating unit is selected from the group consisting of the following structural formulas (IV) or mixtures thereof:

A process for producing a terpene diamine, the process comprising the steps of: 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 having an amino and carboxyl group is obtained, iii) reacting the carboxyl group of the at least one ring-opened terpene lactam having amino and carboxyl group to form 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 form an amino group, so that at least one terpene diamine is obtained and v) obtaining the at least one terpene diamine. A process for producing a terpene diamine, the process comprising the steps of: 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 having an amino and nitrile group is obtained, cc) reducing the nitrile group of the at least one ring-opened terpene lactam having amino and nitrile group to an amino group, so that at least one terpene diamine is obtained and dd) obtaining the at least one terpene diamine. Method according to Claim 8 or 9 in which the at least one terpene diamine obtained in step iv) or cc) is selected from the group consisting of the following structural formulas (V) or mixtures thereof: