CH710304A2 - Polyamides based on terpene lactam. - Google Patents

Abstract

The present invention relates to a process for producing a polyamide, a polyamide thus prepared, a polyamide comprising a terpene repeating unit X 1 -LX 2, a process for producing a terpene diamine and the use of a deprotonated terpene lactam as a catalyst component in the production of a polyamide and a metal lactam ,

Description

The present invention relates to a method for producing a polyamide, a polyamide produced in this way, a polyamide having a terpene repeat unit X <1> -LX <2>, a method for producing a terpene diamine and the use of a deprotonated terpene lactam as a catalyst component in the Production of a polyamide and a metal lactamate.

In order to conserve fossil resources and to reduce greenhouse gas emissions, there is great interest in replacing conventional plastics with those that can be made 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 converted with dicarboxylic acids and amino acids with amino acids. In the latter, the amino group and the carboxyl group are both functional groups required for linkage 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.

[0003] ε-Caprolactam is produced industrially from cyclohexanone and laurolactam from cyclododecanone. The ketone is first converted to the oxime and this oxime is then converted into the lactam by a Beckmann rearrangement. Alternatively, the ketone is converted to the lactam in a single reaction, with oxime formation taking place 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 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 from it.

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

It is therefore the object of the present invention to provide a process for the production of polyamides, wherein renewable raw materials are 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 in particular by the teaching of the independent claims.

In particular, a method for producing a polyamide is provided, 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] In particular, the object is therefore achieved by a method for producing a polyamide, at least one terpene lactam being provided in step a). The expression “providing at least one terpene lactam” means in connection with the present invention 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 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 one amino and one carboxyl group, polymerized with one another, preferably copolymerized.

With the present process and with the present manufactured products, surprisingly, a polyamide is made from renewable raw materials in a simple and inexpensive manner. The polyamides produced by the process according to the invention or the process preferred according to the invention or the polyamides according to the invention or according to the invention are characterized in particular by improved, in particular increased, transparency and / or greater strength. As an alternative or in addition, they are preferably also characterized by higher toughness.

The polyamide is preferably produced in that the at least one terpene lactam is preferably copolymerized 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 the at least one terpene lactam is ring-opened. The polymerization of the at least one terpene lactam, preferably with the further polymerizable components, produces a polyamide in step b) 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, which consists of five carbon atoms, also known as carbon atoms, four carbon atoms are linearly linked to one another, with another carbon atom being covalently bonded to 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 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 conventional chemical reaction known from the prior art , preferably by means of an oxidation, reduction or addition reaction. In order to produce a terpene derivative, it is therefore preferable to convert at least one double bond in a naturally occurring terpene to an epoxide, diol, aldehyde or ketone. To produce a terpene derivative, at least one halogen was therefore preferably added to at least one double bond or at least one double bond was oxidized or epoxidized. Alternatively or additionally preferably, the terpene derivative has been prepared by reacting a terpene ketone with an electrophile in the α position 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 halogen in the a-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 in relation to the keto group. Alternatively or additionally preferably, the terpene derivative has a hydroxyl group in the β position to a keto group. As an alternative or in addition, at least one halogen was preferably added in the α position to an alcohol group or keto group of a naturally occurring terpene to produce a terpene derivative. As an alternative or in addition, at least one carbon in the α double bond was oxidized to an alcohol group or a keto group, or a halogen was added to at least one carbon atom in the α 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, N preferably having a value of 0 to 6.

In connection with the present invention, the term “polyamide” is understood to mean a compound which has monomer units, also referred to as repeat units, at least two of the repeat units being linked to one another via an amide bond. Preference is given to 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 repeat units occurring in the polyamide, each via an amide compound connected. The term “polyamide” includes 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 produced 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 initially formed, which rearranges to form the corresponding terpene lactam.

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

Alternatively, the terpene lactam can preferably be produced 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 oxazirtdin, the compound formed being rearranged to form the corresponding terpene lactam.

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 lactam, so that the polymerization in step b) and the ring opening of the at least two, preferably exactly two, rings result in a branch 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 produced 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 menthol. The terpene ketone, preferably α-pinene, can be prepared by converting a double bond present in a terpene, preferably α-pinene, into the corresponding diol and then splitting off water. The terpene ketone, preferably of α-pinene, can alternatively preferably be prepared by direct conversion of a double bond present in a terpene, preferably of α-pinene, into 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 explained mechanistically. According to a reaction mechanism recognized in the literature, the hydroxyl group of the ketoxime is first protonated. By migration of the trans carbon chain covalently bonded to the carbon atom of the ketoxime group to the nitrogen atom of the ketoxime group, water is split off there. Subsequently, water is attached to the positively charged carbon atom of the resulting 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 produces two different terpene lactams.

In connection with the present invention, the term “activator component” is understood to mean a chemical compound which is intended to start 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 is preferably a lactam having an electrophilic radical, 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 thereof. The activator component is preferably an N-acyl terpene lactam.

In connection with the present invention, 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). A reactive system consisting of activator and catalyst components is therefore 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 a maximum of 100: 1, preferably a maximum of 50: 1, preferably a maximum of 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 from 10,000: 1 to 10: 1, preferably from 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 terpene lactam provided in step a) and the at least one activator component is preferably a maximum of 100: 1, preferably a maximum of 50: 1, preferably a maximum of 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 from 10,000: 1 to 10: 1, preferably from 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 from 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 unblocked with a protecting group, a polyisocyanate or a derivative thereof, a carbodiimide, which can preferably also be in cyclic form. 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).

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

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

[0033] At least one terpene lactam and at least one non-terpene lactam are preferably provided in step a). 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, at the end, the two functional groups preferably being formed by an aromatic, non-aromatic, unsaturated or saturated carbon ring with preferably three to 20 carbon atoms, preferably 5 to 11 carbon atoms, or by a carbon chain with preferably 1 to 20 carbon atoms, preferably 3 to 11 carbon atoms, are connected to one another, optionally at least one carbon atom, preferably a maximum of half of the carbon atoms present in the carbon chain, has been substituted by a heteroatom, the heteroatom being independent has been selected from one another from the group consisting of O, S, Se, NH, NR. The carbon ring and / or the carbon chain is / are preferably unsubstituted.

The at least one non-terpene lactam is preferably ε-caprolactam and / or laurolactam.

In a preferred embodiment, chiral terpene lactams are provided in step a). A single diastereomer of the at least one terpene lactam alone is preferably provided in step a). The terpene lactam of (+) - camphor alone is preferably polymerized as terpene lactam in step b). Alternatively, the terpene lactam alone is preferably polymerized by (-) - camphor as the terpene lactam. Alternatively, the terpene lactam alone is preferably polymerized from (-) - camphor and (+) - camphor as terpene lactam. The polyamide is preferably produced by first polymerizing (-) - camphor alone and, independently of this, polymerizing (+) - camphor alone, and then copolymerizing the (-) - camphor polyamide with the (+) - camphor polyamide, whereby a mixed polymer, also referred to as a blend, is obtained. Alternatively, a mixture of (+) - camphor and (-) - camphor is preferably provided as terpene lactam in step a) and is 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. The terpene lactam provided in step a) can alternatively preferably be obtained from a terpene ketone, the terpene oxime formation taking place 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 are copolymerized in step b).

A process is preferably provided in which the polymerisation in step b) takes place anionically or hydrolytically. In the case of anionic polymerization, an anion, preferably a deprotonated lactam, preferably deprotonated terpene lactam, is used preferably as a catalyst component and preferably in the form of a salt, also referred to as a metal lactamate.

Anionic polymerization is a conventional type of polymerization in the prior art. It is within the skill of the art to set 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, Makromolekulare Chemie, Wiley VCH 2005).

In hydrolytic polymerization, the ring opening of the terpene lactam takes place preferably with the addition of catalytic, stoichiometric or superstoichiometric amounts of protic solvents. In the hydrolytic polymerization, the ring opening of the terpene lactam takes place preferably with the addition of catalytic, stoichiometric or superstoichiometric amounts of water, an aqueous acid, an alcohol, ammonia or an amine. The addition of water, preferably supported by the protonation of the oxygen in the lactam group, opens the ring of the lactam. 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 in a further process step.

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, Bottenbruch / Binsack). In the 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 100 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 using extruders of various types, 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), preference is given to using at least one activator component in addition to the at least one catalyst component, the at least one activator component being an N-acyl terpene lactam. The catalyst component can 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 produced from a cyclic terpene ketone.

The terpene ketone is preferably converted to the terpene lactam by Beckmann rearrangement.

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

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

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

The ketones produced 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, the allylic carbon atom of the α-pinene, β-pinene, δ-pinene or 3-carene is preferably oxidized to the ketone for the preparation of the terpene ketone.

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

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.

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

Polymerization in step b) 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 is preferred.

The polyamide obtained in step c) preferably has a molecular weight Mn 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 mol (each determined by gel permeation chromatography). 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 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 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 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).

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

In the hydrolytic polymerization, preference is given to using protic solvents, preferably alcohols or water, preferably water. The anionic polymerization is preferably carried out free of aprotic solvents, preferably free of any solvents.

In particular, the object of the present invention is achieved by a polyamide which has been produced by polymerizing at least one terpene lactam. The polyamide is preferably produced by a method according to the invention or a method 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 Group consisting of an NH group and a C = O group, the at least one terpene repeating unit having at least one isoprene unit.

The terpene repeat unit X <1> -LX <2> preferably additionally has (4 + n5) if X <1> and X <2> are not an NH group, or (5 + n5) if X 1 and X 2 are an NH group, they have carbon atoms, n having 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 -L-X 2 is preferably a terpene repeat 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 L1 is different from L <2>.

The polyamide preferably has only terpene repeat units as repeat units. The terpene repeating 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 repeating unit being selected from the group consisting of the following structural formulas (III) or mixtures thereof:

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

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

The polyamide according to the invention or produced according to the invention 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 produced from a cyclic terpene with 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 comprises 1 to 100%, preferably 5 to 100%, of the at least one ring-opened terpene lactam (based on all repeat 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 produced according to the invention preferably has a relative viscosity η rel of> 1.5, preferably> 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 produced 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, 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, granules, a powder, a fiber, a plate, a tube, a casing, a shaped or profile piece or the like.

In particular, the technical problem of the present invention is solved in that a method for producing at least one terpenediamine is provided, the method comprising the following steps: i) providing at least one terpene lactam, ii) ring-opening conversion of the provided in step i) at least one terpene lactam, so that at least one ring-opened terpene lactam with amino and carboxyl groups is obtained, iii) conversion of the carboxyl group of the at least one ring-opened terpene lactam with amino and carboxyl groups to form an aldehyde group, so that at least one ring-opened terpene lactam with amino and aldehyde groups is obtained iv) converting the aldehyde group of the at least one ring-opened terpene lactam with amino and aldehyde groups to form an amino group, so that at least one terpenediamine is obtained and v) obtaining the at least one terpenediamine.

Preferably in step iii) the carboxyl group is 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.

In particular, the technical problem of the present invention is solved by providing a method for producing at least one terpene diamine, the method comprising the following steps: aa) providing at least one terpene lactam, bb) implementing the at least one provided in step aa) a terpene lactam with ammonia, so that a ring-opened terpene lactam with amino and nitrile groups is obtained, cc) reducing the nitrile group of the at least one ring-opened terpene lactam with amino and nitrile groups to an amino group, so that at least one terpene diamine is obtained, and dd) obtaining the at least one terpenediamine .

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

In particular, the object of the present invention is achieved by using 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. In addition to using the at least one deprotonated terpene lactam, at least one N-acyl terpene lactam is used as an activator component in the production of a polyamide.

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

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

In a preferred embodiment, all in connection with the inventive or preferred method and / or the inventive or preferred polyamide also apply mutatis mutandis to the method for producing a terpenediamine and / or the use of a deprotonated terpene lactam and / or an N. -Acyl Terpene Lactams.

In particular, the technical problem of the present invention is solved by a metal terpene lactamate. The metal of the metal terpene lactamate is preferably selected from the first three main groups of the periodic table. The metal terpene lactamate is preferably a sodium terpene lactamate or a magnesium terpene lactamate.

Preferred refinements of the present invention emerge from the subclaims.

The present invention is explained in more detail using the following example.

In all of the structural formulas 1 to 108 above, no specific 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 present in structural formulas 1 to 108, then all variants of a possible spatial arrangement of the radicals are included.

Example:

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

In a 250 ml 2-neck flask with a magnetic stirrer, reflux condenser and dropping funnel, 36.2 g of ε-caprolactam (Merck), 10.0 g of the lactam produced from camphor, also referred to as camphor-lactam, are removed with exclusion of air and moisture and 0.361 g acyl caprolactam (activator: Brüggemann C20P) and melted by heating to 200 ° C.

In a dropping funnel, with the exclusion of air and moisture, a mixture of 9.47 g of ε-caprolactam and 3.36 g of sodium lactamate (Brüggemann C10) heated to 80 ° C.-100 ° C. and thus melted is presented and added 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 powdered polymer with about 10% residual moisture in 43 ml of deionized water are refluxed for 24 hours. The suspension is filtered hot, the solid is dried and the thermal properties are determined by dynamic differential calorimetry (DSC). 2.16 g of solid are obtained. The solvent of the mother liquor is removed in vacuo and the residue is also dried. 0.660 g are obtained. The 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 (15)

1. A method of making a polyamide, 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 is obtained and c) Obtaining the polyamide containing at least one ring-opened terpene lactam. 2. The method according to claim 1, wherein the polymerizing according to step b) takes place anionically or hydrolytically. 3. The method according to any one of the preceding claims, wherein at least one catalyst component is added in step b). 4. The method according to any one of the preceding claims, wherein the at least one terpene lactam is produced from a cyclic terpene ketone. 5. The method according to any one of the preceding claims, wherein the cyclic terpene ketone is selected from the group consisting of the following structural formulas (I): 6. The method according to any one of the preceding claims, wherein the at least one terpene lactam is selected from the group consisting of the following structural formulas (II) or mixtures thereof: 7. Polyamide made by polymerizing at least one terpene lactam. 8. Polyamide having 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 and wherein the at least one terpene repeating unit has at least one isoprene unit. 9. Polyamide according to claim 8, wherein the at least one terpene repeating unit is selected from the group consisting of the following structural formulas (III) or mixtures thereof: 10. Polyamide according to one of claims 8 or 9, wherein the at least one terpene repeating unit is selected from the group consisting of the following structural formulas (IV) or mixtures thereof: 11. A method of making a terpene diamine, 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 groups is obtained, iii) converting the carboxyl group of the at least one ring-opened terpene lactam with amino and carboxyl groups to form an aldehyde group, so that at least one ring-opened terpene lactam with amino and aldehyde groups is obtained, iv) converting the aldehyde group of the at least one ring-opened terpene lactam with amino and aldehyde groups to form an amino group so that at least one terpene diamine is obtained and v) obtaining the at least one terpene diamine. 12. A method of making a terpene diamine, the method 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 with amino and nitrile groups is obtained, cc) reducing the nitrile group of the at least one ring-opened terpene lactam with amino and nitrile groups to an amino group, so that at least one terpene diamine is obtained and dd) obtaining the at least one terpene diamine. 13. The method according to claim 11 or 12, wherein the at least one terpenediamine obtained in step iv) or cc) is selected from the group consisting of the following structural formulas (V) or mixtures thereof: 14. Use of at least one deprotonated terpene lactam as a catalyst component in the production of a polyamide. 15. A metal terpene lactamate.