RU2801943C2 - Enriched with 3-caranlactam isomer and polyamide based on it with high optical purity and controlled crystallinity for high-performance applications - Google Patents

Abstract

FIELD: polycaranamides.

SUBSTANCE: invention relates to polycaranamides, which are 3S or 3R-polycaranamide, 3S/3R-co-polycaranamide, to methods for obtaining: a mixture of 3S- and 3R-caranone enriched in isomers from 3-caranepoxide, a mixture of 3S- and 3R-caranoxime enriched in isomers from 3-caranepoxide, enriched in isomers of a mixture of 3S- and 3R-caranlactam from 3-caranepoxide, enriched in isomers of polycaranamide from 3-caranepoxide, 3S- or 3R-caranlactam from 3-carene, as well as to 3S-caranoxime, 3S-caranlactam and a plastic product. 3S- and 3R-polycaranamides are compounds of formulas

and respectively. 3S/3R-co-polycaranamide is a compound of the formula

The present invention provides a method for the production of polyamides from renewable raw materials or by-products, as well as a method for the production of monomers necessary for the production of polyamide and intermediate products for the synthesis of these monomers.

EFFECT: resulting polyamides have improved properties, namely greater transparency and/or strength and/or toughness and/or stereoregularity, in particular for stereo- or enantioselective applications.

26 cl, 83 dwg, 13 tbl, 11 ex

Description

The invention relates to a method for the production of a mixture of 3S- and 3R-caranone enriched with isomers (IUPAC: (1R,4S,6S)-4,7,7-trimethylbicyclo[4.1.0]heptan-3-one and (1R,4R,6S) -4,7,7-trimethylbicyclo[4.1.0]heptan-3-one) from 3S-caranepoxide (IUPAC: (1S,3S,5R,7R)-3,8,8-trimethyl-4-oxatricyclo[5.1. 0.03.5]octane) and 3S-caranone extracted from it, the method for the production of 3S-caranlactam (IUPAC: (1R,5S,7S)-5,8,8-trimethyl-4-azabicyclo[5.1.0]octane-3- it) from (+)-3-carene ((1S,6R)-3,7,7-trimethylbicyclo[4.1.0]hept-3-ene), 3R-caranlactam production process (IUPAC: (1R,5R,7S )-5,8,8-trimethyl-4-azabicyclo[5.1.0]octan-3-one) from (+)-3-carene, and to the following compounds: 3S-caranoxime (IUPAC: (1R,4S,6S )-4,7,7-trimethylbicyclo[4.1.0]heptan-3-one oxime), 3S-caranlactam, 3S-polycaranamide, 3R-polycaranamide and 3S/3R-co-polycaranamide, in particular 3S-caranlactam-3R -karanlactam-co-polycaranamide, 3S-karanlactam-laurinlactam-co-polycaranamide, 3S-karanlactam-caprolactam-co-polycaranamide, 3R-karanlactam-laurinlactam-co-polycaranamide, 3R-karanlactam-caprolactam-co-polycaranamide.

From the point of view of saving fossil resources and reducing greenhouse gas emissions, it is of particular interest to replace conventional polymers, such as polyamide based on fossil raw materials, with those that can be obtained from renewable raw materials. The polyamide is formed by combining difunctional monomers with amino groups and carboxyl groups, preferably activated. In this case, both diamines with dicarboxylic acids and amino acids with amino acids can participate in the reaction. In the latter case, one molecule contains both functional groups necessary for the connection - an amino group and a carboxyl group. Among other things, for the production of polyamides, for example by ring-opening polymerization, lactams such as ε-caprolactam can be used.

Two commercially important fossil-based lactams that are used for polymerization are ε-caprolactam, used for the production of Polyamide-6 (PA6), and laurin lactam, used for the production of polyamide-12. ε-caprolactam is industrially obtained from cyclohexanone, laurinlactam - from cyclododecanone. Here, the ketone is first converted to an oxime, then the oxime is converted via Beckmann isomerization to lactam and also to a monomer for the production of polyamide.

Commercially available bio-based polyamides have so far been produced predominantly from castor oil. The monomers derived from fatty acids lead to the formation of linear, partially crystalline polymer chains (PA11, PA410, PA610, PA1010, PA10.12) with properties comparable to fossil-based polyamides.

The glass transition temperature (Tg) of commercially available polyamides based on fatty acids is generally less than 60°C. The ß-pinene based polyamide described by Winnacker (M. Winnacker, J. Sag, A. Tischner, B. Rieger, Macromol. Rapid Commun. 2017, 38,1600787) has a Tg of 160°C and a melting point (Tm) of 264°C , however, only reaches a molar mass of about 24 kDa. Menthon lactam has so far only been able to convert to oligomers. The currently known polyamides based on terpenes and fatty acids are partially crystalline. In addition, polyamides based on terpenes and fatty acids are still being produced, either predominantly with a low molar mass or with a low glass transition temperature and, consequently, limited application possibilities. Methods for the synthesis of the corresponding monomers in most cases cannot be implemented on an industrial scale (based on terpenes).

It is advantageous when, on the one hand, the renewable raw material used for the production of monomers does not compete with the production of food products, on the other hand, in itself, does not require special cultivation for this purpose. It would be particularly advantageous if the renewable raw material in the production of another product from renewable raw materials was accumulated as a by-product or waste. For example, in the production of cellulose, large amounts of terpenes are formed, in particular, these are by-products of the production of cellulose from wood. In this regard, you can refer to the document DE 10 2014 221 061 A1.

In addition, a disadvantage of currently known methods for the production of polyamides from renewable raw materials is that the monomers used for the production of polyamide or intermediate products of the synthesis of these monomers are often not chemically pure and/or cannot be obtained as pure isomers. In addition, the disadvantage is that the application temperature of the polyamide often allows only a small number of uses, and the achievable molar mass is low. In addition, under certain conditions, it is a disadvantage that the optical purity, ie (hereinafter abbreviated) tacticity, as well as the crystallinity of the polyamide, cannot be purposefully controlled.

In principle, purification methods are available in the field of chemistry, for example chromatographic separation, suitable for separating isomers from each other, in particular isomeric intermediates in the production of monomers or the isomeric monomers themselves, however, very often these methods are labor intensive and costly. Therefore, the corresponding polyamides can be very expensive compared to fossil-based polyamides.

Thus, the object of the present invention is to provide a method for the production of polyamides from renewable raw materials or by-products, as well as a method for the production of monomers necessary for the production of polyamide and intermediate products for the synthesis of these monomers, which do not suffer from the disadvantages of the prior art. In particular, it should be possible to obtain, by means of the process provided, polyamides which, compared to known polyamides from non-renewable or petroleum raw materials, have improved properties, preferably greater transparency and/or strength and/or toughness and/or stereoregularity, in particular for stereo- or enantioselective application.

The problem of the present invention is solved, in particular, by the technical solution of paragraph 1, as well as other dependent claims.

The present invention solves the stated technical problem also by providing a polycaranamide, wherein the polycaranamide is a 3S-polycaranamide of the formula (with n repeating units):

or 3R-polycaranamide formula (with n repeating units):

The invention also relates to 3S-3R-co-polycaranamide of the formula (with a, b and n repeating units):

Said polycarenamides can in a preferred embodiment be obtained by the method of the present invention, in particular using the method according to the invention, in which the polycaranamides according to the invention are obtained from 3-carene, preferably 3-carene epoxide, in particular the mixtures enriched with 3S isomers obtained therefrom. -caranon and 3R-caranon. A significant contribution of the present invention is the preparation from 3-carene or 3-caranepoxide by the method according to the invention of a precursor for the synthesis of co-polycaranamide, in particular 3S-caranone for the production of 3S-polycaranamide. In a preferred embodiment of the invention, 3S-caranone-rich mixtures are provided, in particular a 3S-caranone-enriched mixture, from which 3S-caranoxime and 3S-caranlactam, precursors of 3S-polycaranamide or 3S-co-polycaranamide, can advantageously be prepared.

The present invention also relates to a process for the production of an isomer-enriched mixture of 3S-caranone and 3R-caranone from 3-caranepoxide, comprising the following steps: a) preparing a reaction mixture containing 3-caranepoxide and at least one acid catalyst, b ) carry out the isomerization of 3-caranepoxide in the reaction mixture at a temperature of -40° C. to 140° C. and c) obtain an isomer-enriched mixture with an isomer ratio of at least 80% 3S-caranone or 3R-caranone (relative to total caranone) .

The invention preferably provides that the reaction mixture prepared in step a) of the process additionally contains a first organic solvent.

In particular, the present invention relates to a process for the production of an isomer-enriched mixture of 3S-caranone and 3R-caranone from 3-caranepoxide, comprising the following steps: a) preparing a reaction mixture containing 3-caranepoxide, at least one acid catalyst and , at least the first organic solvent, b) carry out the isomerization of 3-caranepoxide in the reaction mixture at a temperature of from -40°C to 140°C and c) obtain an isomer-enriched mixture with an isomer ratio of at least 80% 3S-caranone or 3R-caranone (relative to the total amount of caranone). Provided according to the invention, the provision of a reaction mixture containing 3-caranepoxide, at least one acid catalyst and, in a preferred embodiment, at least a first organic solvent, preferably corresponds to mixing 3-caranepoxide, at least one acid catalyst and optionally at least a first organic solvent. In the reaction mixture thus obtained, according to step b) of the process, the 3-caranepoxide is converted into the isomer-enriched mixture obtained in step c) of the process with an isomer ratio of at least 80% 3S-caranone or at least 80% 3R -caranone (in each case relative to the total amount of 3S- and 3R-caranone, hereinafter also abbreviated as "caranone"), while the 3-caranepoxide is converted into 3S-caranone and 3R-caranone. The isomer-containing mixture may preferably be purified or isolated.

Preferably, at least one acid catalyst is a Lewis acid, particularly preferably a metal salt of a strong acid, in particular a metal salt of an acid stronger than trifluoroacetic acid, with a pKs of 0.23, preferably a metal salt of the third to fifth period , in particular 4-13 groups, in particular 7-12 groups, in particular with an oxidation state of 2 to 3.

Preferably, at least the first organic solvent is an aliphatic or aromatic solvent, in particular a solvent consisting only of hydrocarbons without heteroatoms, in particular a solvent comprising 4-10 carbon atoms, in particular 5-7 carbon atoms, with boiling point from 30°C to 126°C, preferably from 60°C to 81°C, in particular with a relative polarity of less than 0.134 (dioxane).

The invention preferably provides that the conversion of the 3-caranepoxide in step b) of the process into an isomer-enriched mixture of S- and R-caranone takes place at a temperature of from 0°C to 100°C, preferably from 20°C to 80°C, preferably , from 40°C to 65°C, in particular from 45°C to 60°C, in particular from 48°C to 53°C, in particular from 50°C to 60°C, in particular 50 °C or 60°C.

In addition, according to the invention, it is preferably provided that the conversion of the 3-caranepoxide in step b) of the process takes place via Meinwald isomerization. In particular, it is envisaged that the Meinwald isomerization occurs according to a concerted mechanism without intermediate steps or a mechanism with intermediate steps, in particular with intermediates (1R,6S)-7,7-dimethyl-4-methylenebicyclo[4.1.0]heptane-3- ol and (1R,6S)-4,7,7-trimethylbicyclo[4.1.0]hept-3-en-3-ol. One theory, however, without a definite reference to it, is the stereoselective isomerization of Mainvaln 3S-caranepoxide in stage b) of the process, obtaining in stage c) of the process an isomer-enriched mixture containing at least 80% 3S-caranone relative to the total amount of caranone, is that the reaction proceeds, preferably, according to an agreed mechanism.

According to the invention, it is preferably provided that the mixture enriched in isomers obtained in step c) of the process is characterized by an isomer ratio of at least 85%, at least 90% or at least 95% 3S-caranone or 3R-caranone ( relative to the total amount of caranon).

Thanks to the process according to the invention for the production of an isomer-enriched mixture of 3S-caranone and 3R-caranone, it is possible to economically obtain intermediate products, in particular 3-caranone isomers, from which the monomers according to the invention necessary for the production of polyamide can be obtained. According to the invention, in a preferred embodiment, the reaction can be directed such that the appropriate target intermediate, either 3S-caranone or 3R-caranone, is present in a high percentage of the resulting isomer-enriched mixture. The monomers according to the invention required for the production of the polyamide according to the invention can be advantageously, rapidly and efficiently obtained from an isomer-enriched mixture of 3S-caranone and 3R-caranone by means of other intermediates, 3-caranoxime and 3-caranlactam. The thermoplastic terpene-based polyamides according to the invention, which can be obtained from them, meet high thermal requirements and have a high molar mass. In addition, the productivity of the process for the production of the polymers of the invention is potentially comparable to commercially available methods for the production of polymers from fossil raw materials. The production process according to the invention, herein also referred to as the synthesis route, is preferably so controllable as to produce either purely crystalline or completely amorphous polyamide. Using the production process according to the invention, the corresponding 3-carene-based lactam can be obtained, i.e. the monomer of the polyamide according to the invention, separated into two diastereomers, which are converted to a polyamide either completely amorphous or partially crystalline, thus satisfying the requirements of various applications. The polyamide from 3S-caranlactam is partially crystalline, the polyamide from 3R-caranlactam is amorphous. The molar mass of both polymers can reach more than 50 kDa or 100 kDa, preferably more than 10 kDa or 33 kDa. The polyamides obtained according to the invention preferably have a high optical purity, are transparent in a preferred embodiment and are preferably characterized by stereoregularity, which can be advantageously used, in particular, for stereo- or enantioselective applications, for example, for chiral stationary phases in high-performance liquid chromatography (high pressure liquid chromatography, HPLC) or chiral membranes. The polyamides obtainable according to the invention are, in the preferred embodiment, in the form of their homopolymers, isotactic.

In the context of the present invention, the term 3-carene refers to both (1S, 6R)-(+)-3-carene and the (1R, 6S)-(-)-3-carene isomer. Preferably, (1S,6R)-(+)-3-carene is used as the 3-carene. The substances and products obtained according to the invention from 3-carene have, respectively, either the stereoisomer configuration (1S, 6R)-(+)- or the stereoisomer configuration (1R, 6S)-(-)-, preferably the stereoisomer configuration (1S, 6R )-(+)-.

In the context of the present invention, the term "amorphous polymer" refers to a polymer in which, when thermally analyzed by differential scanning calorimetry (differential scanning calorimetry (DSC)), according to the following method (3), up to the decomposition temperature, only one glass transition temperature is observed or no melting point is observed; or according to methods (3.1) and (3.2) below, up to a temperature of 320°C (method 3.1) or decomposition temperature (method 3.2), only one glass transition temperature is observed or no melting point is observed.

In the context of the present invention, the term "partially crystalline polymer" means a polymer in which, when thermally analyzed by differential scanning calorimetry (DSC) according to the following methods (3) or (3.1) or (3.2), up to the decomposition temperature, both the glass transition temperature and melting temperature.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) according to the invention are preferably determined by the following methods (4.1) or (4.2), preferably by method (4.2).

In the context of the present invention, polydispersity refers to the coefficient obtained by dividing the weight average molecular weight (also referred to as weight average) (Mw) by the number average molecular weight (Mn) - (Mw/Mn), while, (Mw) and (Mn) are determined according to the methods ( 4.1) or (4.2), in particular, according to the method (4.2).

In the context of the present invention, the term "water absorption" refers to a decrease in quantitative comparison with PA6 (polyamide 6) increase in the weight of the polyamide sample after conditioning with water compared to the dry state, which can be determined according to the following method (5) in a qualitative comparison with PA6.

In the context of the present invention, a polyamide is "transparent" when, according to the following method (6), a film can be produced that is, in qualitative comparison with PA6 and PA12, colorless transparent to opaque.

In the context of the present invention, the term "intermediate" means a compound which is obtained from a starting compound, represented in particular by 3-carene or 3-caraneopoxide, following the first step of the process and at least the second step of the process, for example, also additional process steps are converted into the final product, represented, in particular, by 3-caranlactam or the corresponding polyamide. In the context of the present invention, the intermediate, in particular 3-caranone and 3-caranoxime, is also a semi-finished product from the 3-caranepoxide of the monomer 3-caranlactam.

In addition, in the context of the present invention, the term "isomer-rich mixture" refers to a mixture of two diastereomeric compounds, wherein one of the diastereomeric compounds occurs more frequently in the mixture than the other compound. The isomer in the context of the present invention is preferably a diastereomeric compound.

In particular, in a preferred embodiment of the present invention, the "isomer-enriched mixture" of the present invention contains at least 80, at least 85, at least 90, at least 95, at least 98, at least at least 99% (in each case, relative to the amount of all isomers) of one isomer, in particular one of the diastereomeric compounds.

The expression "isomer-enriched mixture of 3S-caranone and 3R-caranone" (with respect to the specifically indicated enrichment also enriched with 3S- or 3R-caranone mixture or mixture of isomers) means that said isomer-enriched mixture contains the named diastereomeric compounds, in particular contains , especially, in particular, contains more than 50, in particular more than 60, in particular more than 70, in particular more than 80, in particular more than 90, in particular more than 95, in particular more than 99% ( dry matter weight of diastereomeric compounds relative to the dry matter weight of the mixture), in particular, consists of diastereomeric compounds. With respect to other isomer-enriched mixtures provided by the present invention, in particular 3S- and 3R-caranoxime and 3S- and 3R-caranlactam, it is also true that the term "enriched mixture" means that the mixture contains mainly the corresponding reducible isomers, preferably, in an amount of more than 50, in particular more than 60, in particular more than 70, in particular more than 80, in particular more than 90, in particular more than 95, in particular more than 99 wt%. (in each case, the dry matter weight of the diastereomeric compounds relative to the dry matter weight of the mixture), in particular, the mixture consists of diastereomeric compounds.

By means of the method according to the invention for the production of an isomer-enriched mixture of 3S-caranone and 3R-caranone, the desired isomer can be obtained in high yield and with a purity of at least 80%, in particular at least 85%, in particular at least at least 90%, in particular at least 95%, in particular at least 99% of one isomer (in each case, relative to the amount of both isomers), in particular without significant by-products, in particular by-products product that cannot be converted or isomerized to the desired isomer.

Moreover, it is an advantage of the process according to the invention that the mixture of isomers enriched in 3S-caranone can be obtained in only one reaction step, starting from the epoxide, without the need for intermediate steps.

The polyamides synthesized from 3-carene according to the invention, in addition to an increased proportion of the amorphous component, are characterized by a significantly increased glass transition temperature Tg from 100 to 130°C, in particular from 105 to 125°C, in particular from 105 to 115°C, from 110 to 120 °C, in particular, about 115°C instead of about 60°C for most commercially available polyamides from renewable raw materials. The values observed for the polyamide and co-polyamide according to the invention can possibly, without being bound by a particular theory, be explained by the fact that the polyamides obtained from lactams, i.e. monomers according to the invention, based on the condensed 3-carene terpene, due to the ring remaining in the polymer chain is characterized by chain entanglement, as a result of which softening (glass transition) occurs only at a higher temperature. This expands the temperature range in which these polymers can be used.

Due to the structure of the 3-carene molecule, when it is converted to lactam, potentially two different diastereomers are formed. According to the invention, in certain embodiments, it is possible to synthesize both isomers with high stereoselectivity in a manner that meets production and economic requirements.

Preferably obtained selectively from 3R-caranlactam, the 3R-polycaranamide according to the invention (also referred to as 3R-polyamide) is amorphous, preferably completely amorphous, and has a glass transition temperature of from about 100 to 130° C., in particular from 105 to 125° C, in particular from 110 to 120°C. At the same time, the material has properties hitherto unknown for bio-based polyamides of industrial interest.

Preferably also selectively obtained from 3S-caranlactam, the 3S-polycaranamide according to the invention - with a rotated new stereocenter - is partially crystalline and is characterized by a melting point Tm in the range from 230 to 290°C, in particular from 240 to 285°C, in particular from 260 to 290°C, while the glass transition temperature also lies in the range from 100 to 130°C, in particular from 105 to 125°C, in particular from 110 to 120°C. The crystalline structures present in the molecule in addition to the amorphous regions make it possible to use them at even higher temperatures.

In addition, the 3S-caranlactam according to the invention in another preferred embodiment is characterized in that the 3S-caranlactam can be copolymerized with other lactams, preferably caprolactam (CL) or laurin lactam (LL). At the same time, 3S-caranlactam is preferably incorporated into co-polycaranamide by at least 1%, in particular at least 10%, in particular at least 50%, in particular by at least 70%, in particular by at least 80% and up to 100% of the maximum value set as the quantitative ratio of monomers at the beginning of the polymerization. Thus, the invention also relates to 3S-co-polycaranamide, which is or can be obtained from 3S-caranlactam and at least one other lactam, preferably 3R-caranlactam, caprolactam and/or laurinlactam.

The 3S-caranlactam-laurinlactam-co-polycaranamides according to the invention are characterized in a preferred embodiment in that amorphous phases become pronounced as the proportion of 3S-caranlactam incorporated is increased. This makes it possible to control the crystallinity. In addition, in a preferred embodiment, the 3S-caranlactam-laurinlactam-co-polycaranamides are characterized in that higher Tg's are achievable by increasing the proportion of 3S-caranlactam incorporated. This makes it possible to use them at higher temperatures compared to PA12 (polyamide 12).

The 3S-caranlactam-caprolactam-co-polycaranamides according to the invention are preferably characterized in that amorphous phases become pronounced as the proportion of 3S-caranlactam incorporated is increased. This makes it possible to control the crystallinity. In addition, in a preferred embodiment, the 3S-caranlactam-laurinlactam-co-polycaranamides are characterized in that higher Tg's are achievable by increasing the proportion of 3S-caranlactam incorporated. This makes it possible to use them at higher temperatures compared to PA6.

In addition, the 3R-caranlactam according to the invention in a preferred embodiment is characterized in that the 3R-caranlactam can be copolymerized with other lactams, preferably caprolactam or laurin lactam. At the same time, 3R-caranlactam is preferably incorporated into the co-polycaranamide by at least 1.0%, in particular by at least 10%, in particular by at least 50%, in in particular by at least 70%, in particular by at least 80% and up to 100% of the maximum value set as the quantitative ratio of monomers at the start of polymerization. Thus, the present invention also relates to 3R-co-polycaranamide, which is or can be obtained from 3R-caranlactam and at least one other lactam, preferably 3S-caranlactam, caprolactam and/or laurinlactam.

The 3R-caranlactam-laurinlactam-co-polycaranamides according to the invention are characterized in a preferred embodiment in that amorphous phases become pronounced as the proportion of 3R-caranlactam incorporated is increased. This makes it possible to control the crystallinity. In addition, in a preferred embodiment, the 3S-caranlactam-laurinlactam-co-polycaranamides are characterized in that higher Tg's are achievable by increasing the proportion of 3R-caranlactam incorporated. This makes it possible to use them at higher temperatures compared to PA12.

The 3R-caranlactam-caprolactam-co-polycaranamides according to the invention are characterized in a preferred embodiment in that amorphous phases become pronounced as the proportion of incorporated 3R-caranlactam increases. This makes it possible to control the crystallinity. In addition, in a preferred embodiment, the 3R-caranlactam-laurinlactam-co-polycaranamides are characterized in that higher Tg's are achievable by increasing the proportion of 3R-caranlactam incorporated. This makes it possible to use them at higher temperatures compared to PA6.

The following tables 1a) and 1b) present the preferred properties of the 3R- and 3S-polycaranamides according to the invention, as well as their copolymers and copolymers with laurin lactam and caprolactam.

Table 1a: Properties of 3S-polycaranamide, 3R-polycaranamide, 3S-caranlactam-3R-caranlactam-co-polycaranamide, 3S-caranlactam-laurinlactam-co-polycaranamide and 3S-caranlactam-caprolactam-co-polycaranamide of the invention (according to methods ( 3.1), (3.2) and (4.2))

Polymer _Tg (range, °C) _Tm (range, °C) M _w , kDa M _n , kDa 3S-polycaranamide (partially crystalline) 105-120 230-290, in particular 260-290 16.2 10.2 3R-polycaranamide (amorphous) 105-120 No 64.7 33.0 3R-/3S-Co-polycaranamide (R:S=1:3) 105-120 210-250 15.0 10.4 3S-caranlactam-laurinlactam-co-polycaranamide
(embedding 3S/LL=1:1.4) 45-65 No 15.6 10.0 3S-karanlactam-caprolactam-co-polycanalamide
(embedding 3S/CL=1: 1.1) 50-100, in particular 50-70 No 17.3 12.1

Additional parameters of the inventive polyamides can be derived from the GPC (gel permeation chromatography) curves shown in FIG. 78 (3S-polycaranamide), FIG. 79 (3R-polycaranamide) and FIG. 80 (3R/3S-co-polycaranamide).

Table 1b: Properties of 3S-polycaranamide, 3R-polycaranamide and 3S-caranlactam-3R-caranlactam-co-polycaranamide according to the invention (according to methods (3) and (4.1))

Polymer Tg (range, °C) Tm (range, °C) Mw, g/mol Mn, g/mol 3S-polycaranamide (partially crystalline) 110-120 260-290 6.5∙10 ⁴ 1.4∙10 ⁴ 3R-polycaranamide (amorphous) 110-120 No 3.0∙10 ⁵ 1.1∙10 ⁵ 3S/3R-co-polycaranamide (R:S=2:1) 110-120 No 1.1∙10 ⁵ 3.2∙10 ⁴

Additional parameters of the polyamides according to the invention can be derived from the GPC curves shown in FIG. 51-60 (3S-polycaranamide), FIG. 62-71 (3R-polycaranamide), FIG. 72 (3R/3S-co-polycaranamide), FIG. 73-75 (3S-caranlactam-laurinlactam-co-polycaranamide) and FIG. 76-77 (3S-caranlactam-3R-caranlactam-co-polycaranamide).

The 3S-polycaranamide according to the invention (also referred to as 3S-polyamide) is in a preferred embodiment characterized in that the 3S-polycaranamide has a glass transition temperature or a glass transition temperature (Tg) range of 100°C to 130°C, in particular 105°C to 125°C, in particular from 110°C to 120°C, melting point or melting point range (Tm) from 230°C to 300°C, in particular from 230°C to 290°C, in particular from 250° C. to 300° C., in particular from 255° C. to 295° C., in particular from 260° C. to 290° C. and in a preferred embodiment has a number average molecular weight (Mn) of 5.5 x 10 ⁴ g/mol up to 7.5·10 ⁴ g/mol, in particular 6.5·10 ⁴ g/mol and, in a preferred embodiment, a weight average molecular weight (Mw) from 0.4·10 ⁴ g/mol to 2.4 10 ⁴ g/mol, in particular 1.4 10 ⁴ g/mol (Mn and Mw are measured by method (4.1)).

The 3S-polycaranamide according to the invention (also referred to as 3S-polyamide) is in a preferred embodiment characterized in that the 3S-polycaranamide has a glass transition temperature or a glass transition temperature (Tg) range of 100°C to 130°C, in particular 105°C to 125°C, in particular from 110°C to 120°C, melting point or melting point range (Tm) from 230°C to 300°C, in particular from 230°C to 290°C, in particular from 250° C. to 300° C., in particular from 255° C. to 295° C., in particular from 260° C. to 290° C. and in a preferred embodiment has a number average molecular weight (Mn) of 1.0 kDa to 100 kDa, in particular from 5 kDa to 50 kDa, in particular from 10 kDa to 70 kDa and, in a preferred embodiment, a weight average molecular weight (Mw) from 1.0 kDa to 200 kDa, in particular from 5 kDa to 50 kDa, in particular from 5 kDa to 25 kDa, in particular from 15 kDa to 110 kDa (Mn and Mw are measured by method (4.2)).

Preferably, the 3S-polycaranamide according to the invention can be obtained by one of the methods of the present invention. In addition, in a preferred embodiment, the 3S-polycaranamide according to the invention, in the preferred embodiment after polymerization by anionic ring-opening polymerization, in particular according to examples 7.1.1 to 7.1.11, is characterized by a polydispersity (PD) of 1.0 to 10, in particular from 1.0 to 5, in particular from 1.0 to 2.5, in particular from 1.0 to 1.3.

The 3R-polycaranamide according to the invention is preferably characterized in that the 3R-polycaranamide has a glass transition temperature (Tg) of 100°C to 130°C, in particular 105°C to 125°C, in particular 110°C to 120°C and in a preferred embodiment is characterized by a number average molecular weight (Mn) from 2.0·10 ⁵ g/mol to 4.0·10 ⁵ g/mol, in particular 3.0·10 ⁵ g/mol and, in a preferred embodiment, a weight average molecular weight (Mw) from 0.1 x 10 ⁵ g/mol to 2.1 x 10 ⁵ g/mol, in particular 1.1 x 10 ⁵ g/mol (Mn and Mw are measured by the method (4.1)).

The 3R-polycaranamide according to the invention is preferably characterized in that the 3R-polycaranamide has a glass transition temperature (Tg) of 100°C to 130°C, in particular 105°C to 125°C, in particular 110°C to 120°C and in a preferred embodiment is characterized by a number average molecular weight (Mn) from 1.0 kDa to 100 kDa, in particular from 10 kDa to 70 kDa and, in a preferred embodiment, a weight average molecular weight (Mw) from 1.0 kDa up to 200 kDa, in particular from 15 kDa to 110 kDa (Mn and Mw are measured by method (4.2)).

Preferably, the 3R-polycaranamide according to the invention can be obtained by one of the methods of the present invention. In addition, in a preferred embodiment, the 3R-polycaranamide according to the invention, in the preferred embodiment after polymerization by anionic ring-opening polymerization, in particular according to examples 7.2.1 to 7.2.10, has a polydispersity (PD) of 1.0 to 10, in particular from 1.0 to 5, in particular from 1.0 to 2.5, in particular from 1.0 to 1.3.

The 3S/3R-co-polyamide according to the invention, also referred to as 3S-caranlactam-3R-caranlactam-co-polycaranamide, is preferably characterized in that the 3S/3R polyamide has a glass transition temperature (Tg) of 100° C. to 130° C., in particular from 105°C to 125°C, in particular from 110°C to 120°C, melting point from 250°C to 300°C, in particular from 255°C to 295°C, in particular, from 260°C to 290°C and in a preferred embodiment is characterized by a number average molecular weight (Mn) from 2.2·10 ⁴ g/mol to 4.2·10 ⁴ g/mol, in particular 3.2·10 ⁴ g/mol and, in a preferred embodiment, a weight average molecular weight of 0.1 x 10 ⁵ g/mol to 2.1 x 10 ⁵ g/mol, in particular 1.1 x 10 ⁵ g/mol (Mn and Mw measured by method (4.1)).

The 3S/3R-co-polyamide according to the invention, also referred to as 3S-caranlactam-3R-caranlactam-co-polycaranamide, is preferably characterized in that the 3S/3R polyamide has a glass transition temperature (Tg) of 100° C. to 130° C., in particular from 105°C to 125°C, in particular from 110°C to 120°C, melting point from 250°C to 300°C, in particular from 255°C to 295°C, in particular, from 260°C to 290°C and in a preferred embodiment is characterized by a number average molecular weight (Mn) from 1.0 kDa to 100 kDa, in particular from 10 kDa to 70 kDa and, in a preferred embodiment, a weight average molecular weight (Mw ) from 1.0 kDa to 200 kDa, in particular from 15 kDa to 110 kDa (Mn and Mw are measured by method (4.2)).

Preferably, according to the invention 3S-caranlactam-3R-caranlactam-co-polycaranamide can be obtained by one of the methods of the present invention. Furthermore, in a preferred embodiment, the 3S-caranlactam-3R-caranlactam-co-polycaranamide according to the invention, in the preferred embodiment after polymerization by ring-opening anionic polymerization, in particular according to Example 7.3.2, is characterized by a polydispersity (PD) of 1.0 to 10, in particular 1.0 to 5, in particular 1.0 to 2.5, in particular 1.0 to 1.3.

The 3S-caranlactam-laurinlactam-co-polycaranamide according to the invention is preferably characterized in that the glass transition temperature (Tg) at a ratio of 3S-caranlactam:laurinlactam=1:1.4 in 3S-caranlactam-laurinlactam-co-polycaranamide lies in the range from 45°C to 65°C, in particular from 50°C to 60°C, according to the DSC method (3.2) there is no melting point and, in the preferred embodiment, the number average molecular weight (Mn) lies in the range from 1.0 kDa to 100 kDa, in particular from 10 kDa to 70 kDa, and in the preferred embodiment, the weight average molecular weight is from 1.0 kDa to 200 kDa, in particular from 15 kDa to 110 kDa (Mn and Mw are measured by the method (4.2 )), and, preferably, can be obtained by one of the methods of the present invention.

The 3S-caranlactam-laurinlactam-co-polycaranamide according to the invention is preferably characterized in that the glass transition temperature (Tg) at a ratio of 3S-caranlactam:laurinlactam=1:2 in 3S-caranlactam-laurinlactam-co-polycaranamide lies in the range from 35° C to 55°C, in particular from 40°C to 50°C, according to the DSC method (3.2) there is no melting point and, in the preferred embodiment, the number average molecular weight (Mn) lies in the range from 1.0 kDa to 100 kDa , in particular from 10 kDa to 70 kDa, and in a preferred embodiment, the weight average molecular weight is from 1.0 kDa to 200 kDa, in particular from 15 kDa to 110 kDa (Mn and Mw are measured by method (4.2)) , and, preferably, can be obtained by one of the methods of the present invention.

In addition, in a preferred embodiment, the 3S-caranlactam-laurinlactam-co-polycaranamide according to the invention, in the preferred embodiment after polymerization by anionic ring-opening polymerization, in particular according to examples 8.1.1 to 8.1.3, is characterized by polydispersity (PD ) from 1.0 to 10, in particular from 1.0 to 5, in particular from 1.0 to 2.5, in particular from 1.0 to 1.3.

The 3S-caranlactam-caprolactam-co-polycaranamide according to the invention is preferably characterized in that the glass transition temperature (Tg) at a ratio of 3S-caranlactam:caprolactam=1:4.6 in 3S-caranlactam-caprolactam-co-polycaranamide lies in the range from 50°C to 100°C, in particular 50°C to 75°C, in particular 50°C to 70°C, in particular 58°C to 68°C, according to the DSC method (3.2) the melting point is from 140°C to 220°C, in particular from 155°C to 200°C, and, in a preferred embodiment, the number average molecular weight (Mn) lies in the range from 1.0 kDa to 100 kDa, in particular , from 10 kDa to 70 kDa, and, in a preferred embodiment, the weight average molecular weight is from 1.0 kDa to 200 kDa, in particular from 15 kDa to 110 kDa (Mn and Mw are measured by method (4.2)), and, preferably, can be obtained by one of the methods of the present invention.

The 3S-caranlactam-caprolactam-co-polycaranamide according to the invention is preferably characterized in that the glass transition temperature (Tg) at a ratio of 3S-caranlactam:caprolactam=1:1.2 in 3S-caranlactam-caprolactam-co-polycaranamide lies in the range from 70°C to 100°C, in particular from 80°C to 93°C, according to the DSC method (3.2) there is no melting point and, in the preferred embodiment, the number average molecular weight (Mn) lies in the range from 1.0 kDa to 100 kDa, in particular from 10 kDa to 70 kDa, and in the preferred embodiment, the weight average molecular weight is from 1.0 kDa to 200 kDa, in particular from 15 kDa to 110 kDa (Mn and Mw are measured by the method (4.2 )), and, preferably, can be obtained by one of the methods of the present invention.

In addition, in a preferred embodiment, the 3S-caranlactam-capro-co-polycaranamide according to the invention, in the preferred embodiment after polymerization by anionic ring-opening polymerization, in particular according to examples 8.1.1 to 8.1.3, is characterized by polydispersity (PD ) from 1.0 to 10, in particular from 1.0 to 5, in particular from 1.0 to 2.5, in particular from 1.0 to 1.3.

By appropriate selection of the reaction conditions, it is possible to synthesize with high selectivity from the same starting compound, in particular the preferably natural 3-carene compound, the first isomer of the lactam according to the invention, which, on the basis of its stereochemistry, can be converted into an essentially amorphous polyamide, and also the second isomer of the lactam according to the invention, the polyamide of which is partially crystalline, while both polyamides are characterized by a glass transition temperature in the range from 100°C to 130°C, in particular 110°C, while 3S-caranlactam can be converted to semi-crystalline polyamide, and 3R-karanlactam into amorphous polyamide. The method according to the invention makes it possible to control the crystallinity of polyamides in a targeted manner and to obtain isomer-enriched 3-caranlactam and a polyamide based on it with higher optical purity.

The polyamides according to the invention, due to their chemical resistance, can expand the scope of valuable classes of polyamides. Similar to PA66, mechanically and thermally stressed parts can be produced, such as a coil body, a drilling machine body, an automobile oil pan, etc., and also, due to increased temperature stability, long-term use at temperatures above 100 ° C is possible. Fully amorphous polyamide can also be used in the field of transparent polymers. Combinations of the indicated fields of application are also possible, whereby the field of application of the hitherto known biobased polyamides can be considerably extended.

The invention provides polyamides which are in particular synthesized in the form of 3S-polycaranamide, 3R-polycaranamide, 3S/3R-polycaranamide or co-polycaranamide from at least one caranlactam according to the invention and at least one other lactam.

In the context of the present invention, the polyamides according to the invention, containing the monomers according to the invention, can therefore also be in the form of co-polycaranamides (shortly referred to as co-polyamides).

Thus, the invention also relates to plastic parts which are made or can be made from the polyamides according to the invention, in particular those which consist of or contain the polyamides according to the invention, in particular contain a substantial proportion of polyamide, for example more than 5% , 10%, 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 95% (relative to the total weight of the plastic part).

Preferably, the invention provides that the 3-caranepoxide used in process step a) is 3S-caranepoxide and the isomer-enriched mixture obtained in process step c) is a 3S-caranone-enriched mixture with an isomer ratio of at least 80%, in in particular at least 85%, at least 90% or at least 95% 3S-caranone (relative to the total amount of caranone, hence 3R- and 3S-caranone).

In addition, it is preferred that the 3-caranepoxide used in process step a) is 3R-caranepoxide and the isomer-enriched mixture obtained in process step c) is a 3R-caranone enriched mixture with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% 3R-caranone (relative to the total amount of caranone).

In one of the preferred embodiments of the invention it is provided that the acid catalyst is a Lewis acid or Bronsted acid or a mixture of Lewis acid and Bronsted acid.

In another preferred embodiment of the invention, it is provided that the acid catalyst is a strong Bronsted acid or a Bronsted acid with a pKs of at most 0.7.

It is also preferably provided that the acid catalyst is a Bronsted acid with a pKs of at most 0.7, such as a sulfonic acid, in particular para-toluenesulfonic acid (PTSA), methanesulfonic acid or trifluoromethanesulfonic acid.

Preferably, the acid catalyst is a sulfonic acid.

In addition, it is also preferably provided that the acid catalyst is a Lewis acid with an anion of a strong acid, in particular a sulfonic acid, or an anion such as chlorate, trifluoromethanesulfonate ( ^-OTf ) or perchlorate (ClO4 ^- ).

It is also preferably provided that the acid catalyst is an iron ion Lewis acid, a nickel ion Lewis acid, a copper ion Lewis acid, a cobalt ion Lewis acid or a zinc ion Lewis acid, preferably an iron ion Lewis acid.

It is also preferably provided that the acid catalyst is a Lewis acid with an anion, in particular a strong acid or in particular a strong Bronsted acid or in particular a strong Bronsted acid with a pKs of at most 0.7.

It is also preferably envisaged that anions, in particular strong acids such as sulfonic acids, or an anion such as chlorate or perchlorate, can be used as the Lewis acid anion.

It is also preferably provided that chlorate and/or perchlorate and/or sulfonate are used as the Lewis acid anion, in particular for Lewis acids with iron, nickel, cobalt, copper or zinc ions.

Preferably, Fe(ClO ₄ ) ₂ can be used as the Lewis acid ^. H ₂ O, Ni(ClO ₄ ) ₂ , Co(ClO ₄ ) ₂ , Cu(ClO ₄ ) ₂ or their respective hydrates.

In another preferred embodiment of the invention, the acid catalyst is a Lewis acid, in particular a Lewis acid with an iron, copper, cobalt, nickel or zinc ion, preferably a Lewis acid with an iron ion and an anion, in particular a strong acid, preferably trifluoromethanesulfonate or perchlorate, or a strong Bronsted acid with a pKs of at most 0.7, such as sulfonic acids, in particular p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, or a mixture of the above-mentioned Lewis acids and Bronsted acids.

It is also preferably provided that a zeolite, in particular ZSM-5, is used as the acid catalyst. This has the advantage that the zeolite can be added to the mixture as a separable solid, thus being separated from it by filtration.

In addition, it is preferably provided that an acidic heterogeneous catalyst can be used as an acid catalyst in the gas phase polymerization.

In another preferred embodiment of the invention, it is provided that the first organic solvent provided in the preferred embodiment of the invention is a non-polar solvent or a solvent with a relative polarity of at most 0.310, in particular at most 0.200, preferably at most 0.100.

In another preferred embodiment of the invention it is envisaged that the first organic solvent is in particular a non-polar solvent such as aliphatic or aromatic hydrocarbons, preferably xylene, toluene, cyclohexane, pentane, hexane or heptane.

In another preferred embodiment of the invention it is provided that the first organic solvent is 2-methyl-tetrahydrofuran, tetrahydrofuran, ethyl acetate, chloroform or dichloromethane.

In another preferred embodiment of the invention it is provided that the first organic solvent is a solvent with a relative polarity of at most 0.310, in particular at most 0.200, preferably at most 0.100.

In the context of the present invention, the term "relative polarity" refers to the polarity as described in "Solvents and Solvent Effects in Organic Chemistry", Christian Reichards, Wiley-VCH Publishers, 3rd ed., 2003. The relative polarity values for cyclohexane, hexane, heptane and toluene are presented in the table given in example 1.1 of the invention. For polarity values of other solvents, refer to the Reichards document cited.

In addition, it is preferably provided that the 3-caranepoxide in the reaction mixture according to steps a) and b) of the process is used at a concentration of at least 0.1M, preferably from 0.25M to 5M, in particular from 0.3M up to 3M, particularly preferably from 0.5M to 2M, in particular from 0.75M to 1.5M, in particular 1M. This has the advantage that a low concentration can positively influence both overall selectivity and isomer selectivity.

In a preferred embodiment of the invention, it is provided that at a 3S-caranecopsid conversion of at least 80%, the process is characterized by a selectivity with respect to the total amount of a mixture of 3R-caranone and 3S-caranone of at least 50%, in particular at least 70%, while the mixture of 3R-caranone and 3S-caranone contains at least 80%, preferably at least 85% 3S-caranone.

In addition, it is preferably provided that the acid catalyst in the reaction mixture according to stages a) and b) of the method is used in a concentration of 0.01 mol%. up to 2.0 mol %, relative to the 3-caranepoxide used.

In addition, it is preferably provided that the acid catalyst in the reaction mixture according to stages a) and b) of the method is used in a concentration of 0.01 mol%. up to 2.0% mol., in particular, from 0.05% mol. up to 1.0% mol., in particular, from 0.1% mol. up to 0.5% mol., in particular, from 0.15% mol. up to 0.25 mol%, particularly preferably 0.2% mol. relative to the 3-caranepoxide used.

The reaction time in process step b) is preferably 2 minutes to 25 hours, in particular 5 hours to 24 hours, in particular 5 hours to 20 hours, in particular 30 minutes to 1 hour, in particular , from 10 min to 40 min.

In a preferred embodiment, the invention relates to a process for the production of an isomer-enriched mixture of 3S-caranone and 3R-caranone from 3S-caranepoxide comprising the following steps:

a) prepare a reaction mixture containing 3-caranepoxide, at least one acid catalyst and at least a first organic solvent, wherein the acid catalyst is a sulfonic acid or Lewis acid selected from the group consisting of Fe(ClO ₄ ) ₂ ^. H ₂ O, Ni(ClO ₄ ) ₂ , Co(ClO ₄ ) ₂ , Ni(ClO ₄ ) ₂ or Cu(ClO ₄ ) ₂ , or a mixture of these acids, wherein the first organic solvent is selected from the group consisting of toluene , cyclohexane, pentane, hexane, heptane, 2-methyl-tetrahydrofuran, tetrahydrofuran, ethyl acetate and dichloromethane.

b) carry out the isomerization of 3S-caranepoxide in the reaction mixture at a temperature from -40°C to 140°C and

c) an isomer-enriched mixture is obtained with an isomer ratio of at least 80% 3S-caranone (relative to total caranone).

The invention also relates to the above process for the production of an isomer-enriched mixture of 3S-caranone and 3R-caranone from 3S-caranepoxide, wherein the acid catalyst is a sulfonic acid selected from the group consisting of p-toluenesulfonic acid (PTSA), methanesulfonic acid and trifluoromethanesulfonic acid. acids.

In a particularly preferred embodiment of the invention, the 3-caranepoxide used in process step a) is obtained in process step a1) by epoxidation.

In another preferred embodiment of the invention, it is provided that the starting compound used in step a) of the process is 3S-caranepoxide, which is obtained in step a1a) of the process by epoxidation of 3-carene in the presence of a) a peroxy acid, for example dilute peracetic acid or b) a peroxide, for example, H ₂ O ₂ and an enzyme.

In a preferred embodiment of the invention, the enzyme may be, for example, a lipase, for example lipase B, in particular Candida species, in particular Candida antarctica.

In another preferred embodiment of the invention, it is provided that the starting compound used in process step a) is a 3R-caranepoxide, which is obtained in process step a1b) by epoxidation of 3-carene in the presence of N-bromosuccinimide (NBS), optionally additionally in the presence of a base .

In a particularly preferred embodiment of the invention, it is provided that the isomer-rich mixture obtained in step c) of the process is purified, in particular obtained in isolated form, in particular separated from the acid catalyst and/or the first solvent, and/or, under certain conditions , subjected to additional processing, for example, drying.

If, according to the invention, a mixture enriched in 3S-caranone by at least 80% is obtained from 3S-caranone epoxide, this can, if necessary, be converted into a mixture enriched in 3R-caranone in order to obtain 3R-caranlactam in subsequent steps of the process according to the invention, preferably 3R-polycaranamide. In one of the preferred embodiments of the invention, it is provided that the 3S-caranone-enriched mixture obtained, preferably in step c) of the process from 3S-epoxide, in at least one second solvent in the presence of a base or Bronsted acid in step d) of the process, isomerized with obtaining a mixture enriched with 3R-caranone with an isomer content of at least 50%, in particular at least 60%, in particular at least 70%, in particular at least 80%, in particular, at least 85%, in particular at least 90% or in particular at least 95% 3R-caranone (relative to the total amount of caranone).

Preferably, it is contemplated that the base is potassium hydroxide or sodium hydroxide or another strong base.

Also preferably, it is provided that the base is an alcoholate, in particular methanolate.

Preferably, the Bronsted acid is contemplated to be a Bronsted acid with a pKs of at most 0.7.

It is also preferably provided that the Bronsted acid is a strong Bronsted acid. Preferably, the Bronsted acid is aqueous hydrogen chloride, also referred to as aqueous HCl or hydrochloric acid or sulfuric acid.

Preferably, the Bronsted acid is a sulfonic acid.

Further, it is preferably provided that the second solvent is an aprotic polar solvent with a relative polarity of at least 0.200 or a protic polar solvent with a relative polarity of at least 0.200.

Furthermore, it is preferably provided that the aprotic polar solvent with a relative polarity of at least 0.200 is a solvent such as tetrahydrofuran, ethyl acetate, chloroform, dichloromethane, acetone or acetonitrile, in particular acetone or acetonitrile.

Further, it is preferably provided that the protic polar solvent with a relative polarity of at least 0.200 is a solvent such as water, an alcohol, an amine, a carboxylic acid, or an amide.

Further, it is preferably provided that the protic polar solvent with a relative polarity of at least 0.200 is an alcohol such as methanol, ethanol, propanol or butanol.

The reaction time in process step d) is preferably 2 to 80 hours, in particular 5 to 68 hours, preferably 4 to 12 hours, in particular 4 to 10 hours.

In one of the preferred embodiments of the invention, it is provided that the 3S-caranone enriched mixture obtained, preferably in step c) of the process from 3S-caranepoxide, in at least one second solvent in the presence of, in particular, a strong base or, in particular, strong Brønsted acid with a pKs of at most 0.7 is isomerized in process step d) to obtain a mixture enriched in 3R-caranone with an isomer content of at least 50%, in particular at least 60%, in particular at least 70%, in particular at least 80%, in particular at least 85%, in particular at least 90% or in particular at least 95% 3R-caranone ( relative to the total amount of caranone), while the second solvent is an aprotic polar solvent with a relative polarity of at least 0.200 or a protic polar solvent with a relative polarity of at least 0.200.

In a particularly preferred embodiment of the invention, it is provided that the 3S-caranone enriched mixture obtained, preferably in step c) of the process from 3S-caranepoxide, in at least one second solvent in the presence of, in particular, a strong base or, in particular, strong Brønsted acid with a pKs of at most 0.7, preferably a sulfonic acid solution or a hydrochloric acid solution, preferably a 6% hydrochloric acid solution is isomerized in step d) of the process to obtain a 3R-caranone enriched mixture with an isomer content of at least 50%, in particular at least 60%, in particular at least 70%, in particular at least 80%, in particular at least 85%, in particular at least 90% or in particular at least 95% 3R-caranone (relative to the total amount of caranone), wherein the second solvent is an aprotic polar solvent with a relative polarity of at least 0.200 selected from the group consisting of from tetrahydrofuran, ethyl acetate, chloroform, dichloromethane, acetone and acetonitrile, or a protic polar solvent with a relative polarity of at least 0.200 selected from the group consisting of water, alcohol, in particular methanol, ethanol, propanol, butanol, amine, carboxylic acid or amide.

These embodiments have the advantage that the 3R-caranone can be obtained without significant by-product content, ie with greater overall selectivity. In addition, when sulfonic acid is used as an acid catalyst in process step a), it is advantageous that for isomerization to 3R-caranone in process step d), this sulfonic acid can be used as a catalyst after separation of the solvent.

According to the invention, in one of the processes for the production of an isomer-enriched mixture of 3R-caranone and 3S-caranone, it is particularly preferred that an acid, in particular sulfonic acid or Lewis acid, be used as the acid catalyst in step a) of the process. This embodiment of the invention has the advantage that, after separation of the solvent by distillation, no additional acid needs to be added to catalyze the isomerization to 3R-caranone.

In another preferred embodiment of the invention, it is provided that the isomerized isomerized mixture obtained in step d) of the process is purified, in particular obtained in isolated form, in particular separated from the second solvent and/or acid or base and/or, under certain conditions, the mixture is subjected to additional processing at subsequent stages of the method, for example, drying.

In another embodiment of the invention, it is provided that the isomer-enriched mixture of 3S- and 3R-caranone obtained in step c) or d) of the process in the additional step e) of the process in the presence of at least a third organic solvent, a base and hydroxylamine, preferably hydroxylamine hydrochloride (HONH ₂ .HCl) is converted into a mixture enriched in 3-caranoxime with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% 3S - or 3R-caranoxime (relative to the total amount of caranoxime, that is, 3R- and 3S-caranoxime).

If the mixture enriched in 3R-caranone obtained at the end of process step c) or d) is used in process step e), a mixture enriched in 3R-caranoxime is obtained. If the mixture enriched in 3S-caranone obtained according to step c) of the process is used in step e) of the process, a mixture enriched in 3S-caranoxime is obtained.

Preferably, it is contemplated that the third organic solvent is an organic solvent such as an ether, a nitrile, an alcohol, or a water-organic solvent containing water and one of said organic solvents.

It is also preferably contemplated that the ester is tetrahydrofuran or 2-methyl-tetrahydrofuran.

It is also preferably provided that the nitrile is acetonitrile.

It is also preferably provided that the alcohol is methanol, ethanol or isopropanol.

In a preferred embodiment, the base is sodium acetate (NaOAc).

In one of the preferred embodiments of the invention, it is provided that the isomer-enriched mixture of 3S- and 3R-caranone obtained in step c) or d) of the process is obtained in the next step e) of the process in the presence of at least a third organic solvent selected from the group consisting of from an ether, in particular tetrahydrofuran, 2-methyl-tetrahydrofuran, a nitrile, in particular acetonitrile, an alcohol, in particular methanol, ethanol and isopropanol, or a water-organic solvent containing water and one of the third organic solvents mentioned above, a base and hydroxylamine, preferably hydroxylamine hydrochloride (HONH ₂ .HCl) is converted into a 3-caranoxime enriched mixture with an isomer ratio of at least 80%, in particular at least 85%, at least 90%, or at least 95% 3S- or 3R-caranoxime (relative to the total amount of caranoxime).

The 3-caranoxime-enriched mixture obtained in this way has the advantage that the desired isomer makes up the majority of the mixture, so that the majority of the starting compound can be converted in high yield to the desired product, i.e., the desired intermediate of the desired monomer.

In a particularly preferred embodiment of the invention, it is provided that the mixture enriched in 3-caranoxime obtained in step e) of the process is purified, in particular obtained in isolated form, in particular separated from the third solvent and/or base and/or hydroxylamine, and/or , under certain conditions, the mixture is subjected to additional processing at subsequent stages of the method, for example, drying.

In another embodiment of the invention, it is provided that the mixture enriched in 3-caranoxime obtained in step e) of the process, preferably without prior purification in the next step f) of the process, is polymerized to obtain a mixture enriched in 3-caranlactam with an isomer ratio of at least 80% 3S - or 3R- caranlactam (relative to the total amount of caranlactam, that is, 3R- and 3S-caranlactam).

If the mixture enriched in 3S-caranoxime obtained at the end of step e) of the process is used in step f) of the process, a mixture enriched in 3S-caranlactam, in particular 3S-caranlactam, is obtained. If the mixture enriched in 3R-caranoxime obtained according to step e) of the process is used in step f) of the process, a mixture enriched in 3R-caranlactam, in particular 3R-caranlactam, is obtained.

In one of the preferred embodiments of the invention, it is provided that the 3-caranoxime-enriched mixture obtained in step e) of the process is kept at a given temperature in the next step f1) of the process and, by adding a base and p-toluenesulfonic acid chloride, is polymerized to obtain a mixture enriched in 3-caranolactam with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% of 3S- or 3R-caranlactam (relative to the total amount of caranlactam).

It is also preferably provided that the temperature set in step f1) of the process is from 0°C to 50°C, preferably from 10°C to 40°C, preferably from 5°C to 20°C, in particular from 10°C to 18°C.

It is also preferably provided that the base is an aqueous base.

In addition, it is envisaged that the base is a solution of potassium hydroxide or sodium hydroxide.

It is also preferably provided that the isomerization is a Beckmann isomerization.

In one of the preferred embodiments of the invention, it is provided that the mixture enriched with 3-caranoxime obtained in stage e) of the process is kept at a temperature of from -10°C to 50°C in the next stage f1) of the process, in particular from 5°C to 20° C, in particular from 10° C. to 18° C. and by adding a base, in particular an aqueous base, preferably a solution of potassium hydroxide or sodium hydroxide, and p-toluenesulfonic acid chloride, is converted by Beckmann polymerization into a mixture enriched in 3-caranlactam with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% of 3S- or 3R-caranlactam (relative to the total amount of caranlactam).

However, there is an advantage that the polymerization of 3-caranone via 3-caranoxime to 3-caranlactam can be carried out without an intermediate purification step or solvent change, except in the case of using alcohols as a solvent, in a one-pot method for carrying out stages e) and f), for example, when using acetonitrile as a solvent, hydroxylamine hydrochloride, NaOH, tosyl chloride, so that this method is particularly fast, efficient and cost-effective. In this case, a product yield is obtained comparable to the method in which the stages are carried out with a change of solvent.

In addition, it is preferably provided that the mixture enriched in 3-caranoxime obtained in step e) of the process is kept at a given temperature in the next step f2) of the process and, by adding Lewis acid, in particular strong, is polymerized to obtain a mixture enriched in 3-caranolactam with the ratio isomers of at least 80%, in particular at least 85%, at least 90% or at least 95% of 3S- or 3R-caranlactam (relative to the total amount of caranlactam).

It is also preferably provided that the temperature set in step f2) of the process is 15°C to 100°C, preferably 77°C to 87°C, particularly preferably 82°C.

It is also preferably provided that the boiling point of the solvent is set, wherein the solvent is a solvent in which the 3-caranoxime-enriched mixture obtained in step e) of the process is dissolved or present.

Preferably, it is provided that the solvent in which the 3-caranoxime-enriched mixture obtained in process step e) is dissolved or present is acetonitrile.

In addition, it is preferably provided that the Lewis acid is a strong Lewis acid.

In addition, it is preferably provided that the Lewis acid is In(ClO ₄ ) ₃ ∙n H ₂ O (indium perchlorate n-hydrate) and/or Zn(ClO ₄ ) ₂ ∙n H ₂ O (zinc perchlorate n-hydrate ).

In addition, it is preferably provided that the Lewis acid is In(CF ₃ SO ₃ ) ₃ (indium trifluoromethanesulfonate) and/or Zn(CF ₃ SO ₃ ) ₂ (zinc trifluoromethanesulfonate).

Preferably, it is provided that the mixture enriched in 3-caranoxime obtained in step e) of the process is kept at a temperature of from 77° C. to 87° C., in particular 82° C., in the next step f2) of the process and, preferably adding strong Lewis acid, such as In(ClO ₄ ) ₃ ∙n H ₂ O and/or Zn(ClO ₄ ) ₂ ∙n H ₂ O are isomerized to obtain a 3-caranlactam enriched mixture with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% 3S- or 3R-caranlactam (relative to the total amount of caranlactam), preferably the 3-caranoxime enriched mixture obtained in process step e) dissolved or present in acetonitrile.

In a particularly preferred embodiment of the invention, it is provided that the 3-caranlactam-enriched mixture obtained in step f) of the process is then purified, in particular obtained in isolated form, in particular the base and/or p-toluenesulfonic acid chloride are separated, and/or, under certain conditions, the mixture is subjected to additional processing at subsequent stages of the method, for example, drying.

In one of the preferred embodiments of the invention, it is provided that from the mixture enriched in 3-caranlactam obtained in step f) of the process, preferably without prior purification, in step g) of the process, 3S is obtained by crystallization, for example by distillation, in particular fractional distillation. -caranlactam.

It is also preferably provided that from the 3-caranlactam enriched mixture obtained in process step f) after separation of the 3S-caranlactam, in particular according to process step g), 3R-caranlactam is obtained in the next process step h), preferably by crystallization, for example, by distillation, in particular fractional distillation.

In one of the preferred embodiments of the present invention, it is provided that the 3S-caranlactam, 3R-caranlactam or a mixture of 3R- and 3S-caranlactam obtained in step i) of the process is converted into 3S-polycaranamide, 3R-polycaranamide or 3S/3R-co-polycaranamide, preferably by anionic ring-opening polymerization, cationic ring-opening polymerization, hydrolytic polymerization or polycondensation polymerization.

The present invention also relates to a process for the production of a mixture enriched in 3-caranoxime, comprising the steps a), b), c) according to the invention, in a preferred embodiment of the invention, including steps a1), d) or a1) and d), while obtaining in step c) or d) of the process, the isomer-enriched mixture of 3S- and 3R-caranone is converted in the next step e) of the process in the presence of at least a third organic solvent, a base and hydroxylamine, preferably hydroxylamine hydrochloride (HONH ₂ .HCl) into mixture enriched in 3-caranoxime with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% 3S- or 3R-caranoxime (relative to the total caranoxime).

It is also preferably provided that the third organic solvent is an organic solvent such as an ether, a nitrile, an alcohol, or a water-organic solvent containing water and one of said organic solvents.

It is also preferably contemplated that the ester is tetrahydrofuran or 2-methyl-tetrahydrofuran.

It is also preferably provided that the nitrile is acetonitrile.

It is also preferably provided that the alcohol is methanol, ethanol or isopropanol.

In a preferred embodiment, the base is sodium acetate (NaOAc).

The present invention also relates to a process for the production of a mixture enriched in 3-caranoxime, comprising the steps a), b), c) according to the invention, in a preferred embodiment of the invention, including steps a1), d) or a1) and d), while obtaining in process step c) or d) an isomer-enriched mixture of 3S- and 3R-caranone in the next process step e) in the presence of at least a third organic solvent selected from the group consisting of an ether, in particular tetrahydrofuran, 2-methyl -tetrahydrofuran, nitrile, in particular acetonitrile, alcohol, in particular methanol, ethanol and isopropanol, or a water-organic solvent containing water and one of the third organic solvents mentioned above, a base and hydroxylamine, preferably hydroxylamine hydrochloride (HONH ₂ ∙ HCl) is converted into a mixture enriched in 3-caranoxime with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% 3S- or 3R-caranoxime (relative to the total amount of caranoxime).

The present invention also relates to a process for the production of a mixture enriched in 3-caranlactam, comprising steps a), b), c), e), according to the invention, in a preferred embodiment of the invention, including steps a1), d) or a1) and d), when the 3-caranoxime-enriched mixture obtained in process step e) is isomerized in the next process step f) to obtain a 3-caranlactam-enriched mixture with an isomer ratio of at least 80% 3S- or 3R-caranlactam (relative to total caranlactam).

It is also preferably provided that in the process for producing a 3-caranolactam-enriched mixture, the 3-caranoxime-enriched mixture obtained in step e) of the process in the next step f1) of the process is maintained at a predetermined temperature and, by adding a base and p-toluenesulfonic acid chloride, is polymerized to obtain 3-caranlactam enriched mixture with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% 3S- or 3R-caranlactam (relative to the total caranlactam).

It is also preferably provided that the temperature set in process step f1) is from 5°C to 20°C, in particular from 10°C to 18°C.

It is also preferably provided that the base is an aqueous base.

In addition, it is contemplated that the aqueous base is a solution of potassium hydroxide or sodium hydroxide.

It is also preferably provided that the isomerization is a Beckmann isomerization.

In addition, it is preferably provided that in the process for producing a mixture enriched in 3-caranolactam, the mixture enriched in 3-caranoxime obtained in step e) of the process in the next step f1) of the process is maintained at a temperature of from 5°C to 20°C, in particular from 10 °C to 18°C and by adding a base, in particular an aqueous base, preferably a solution of potassium hydroxide or sodium hydroxide, and p-toluenesulfonic acid chloride, is converted by Beckmann polymerization into a mixture enriched in 3-caranlactam with an isomer ratio of at least , 80%, in particular at least 85%, at least 90% or at least 95% 3S- or 3R-caranlactam (relative to the total amount of caranlactam).

It is also preferably provided that in the process for producing a mixture enriched in 3-caranolactam, the mixture enriched in 3-caranoxime obtained in step e) of the process in the next step f2) of the process is kept at a predetermined temperature and, by adding Lewis acid, in particular a strong one, is polymerized to obtain 3-caranlactam enriched mixture with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% 3S- or 3R-caranlactam (relative to the total caranlactam).

It is also preferably provided that the temperature set in step f2) of the process is 15°C to 100°C, preferably 77°C to 87°C, particularly preferably 82°C.

It is also preferably provided that the boiling point of the solvent is set, wherein the solvent is a solvent in which the 3-caranoxime-enriched mixture obtained in step e) of the process is dissolved or present.

Preferably, it is provided that the solvent in which the 3-caranoxime-enriched mixture obtained in process step e) is dissolved or present is acetonitrile.

In addition, it is preferably provided that the Lewis acid is a strong Lewis acid.

In addition, it is preferably provided that the Lewis acid is In(ClO ₄ ) ₃ .n H ₂ O and/or Zn(ClO ₄ ) ₂ .n H ₂ O.

In addition, it is preferably provided that the Lewis acid is In(CF ₃ SO ₃ ) ₃ and/or Zn(CF ₃ SO ₃ ) ₂ .

It is also preferably provided that the isomerization is a Beckmann isomerization.

It is also preferably provided that, in the process for producing the 3-caranolactam-enriched mixture, the 3-caranoxime-enriched mixture obtained in step e) of the process in the next step f2) of the process is maintained at a temperature of between 77°C and 87°C, in particular 82°C. and by adding, preferably, a strong Lewis acid such as In(ClO ₄ ) ₃ ∙n H ₂ O and/or Zn(ClO ₄ ) ₂ ∙n H ₂ O, isomerize to obtain a 3-caranlactam enriched mixture with an isomer ratio, at least 80%, in particular at least 85%, at least 90% or at least 95% 3S- or 3R-caranlactam (relative to the total amount of caranlactam), while preferably obtained in step e) of the process, the 3-caranoxime-enriched mixture is dissolved or present in acetonitrile.

The present invention also relates to a process for the production of 3S-caranlactam from 3S-caranone, wherein the process comprises steps e) and f), wherein the isomer-enriched mixture of 3S- and 3R-caranone with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% 3S-caranone (relative to the total amount of caranone), and convert into a mixture enriched with 3S-caranoxime with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% 3S-caranoxime (relative to the total amount of caranoxime) , in step f) of the process without separation of the solvent of step e) and without isolation of caranoxime, the mixture is converted into a mixture enriched in 3S-caranlactam with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% of 3S-caranlactam (relative to the total amount of caranlactam), while, in the optional step g) of the process, 3S-caranlactam is separated by crystallization, while alcohol is not used as the third organic solvent in step e) of the process .

The present invention also relates to a process for the production of 3R-caranlactam from 3R-caranone, wherein the process comprises steps e) and f), wherein the isomer-enriched mixture of 3S- and 3R-caranone with an isomer ratio of at least 50%, in particular at least 60%, in particular at least 70%, in particular at least 80%, in particular at least , 85%, in particular at least 90% or in particular at least 95% of 3R-caranone (relative to the total amount of caranone), and converted into a mixture enriched in 3R-caranoxime with an isomer ratio of at least 50%, in particular at least 60%, in particular at least 70%, in particular at least 80%, in particular at least 85%, in particular at least 90% or in particular at least 95% of 3R-caranoxime (relative to the total amount of caranoxime), in step f) of the process without separation of the solvent of step e) and without isolation of caranoxime, is converted into a mixture enriched in 3R-caranoxime with an isomer ratio according to at least 50%, in particular at least 60%, in particular at least 70%, in particular at least 80%, in particular at least 85%, in particular at least 90% or in particular at least 95% of 3R-caranlactam (relative to the total amount of caranlactam), optionally in process step h) after separation of 3S-caranlactam by crystallization, according to process step f) 3R-caranlactam, while alcohol is not used as the third organic solvent in step e) of the process.

The present invention also relates to a process for the production of 3S-polycaranamide, 3R-polycaranamide or 3S/3R-co-polycaranamide, as well as polyamides obtained by this process, in particular the 3S-caranlactam, 3R-caranlactam or 3S mixture obtained according to the invention - and 3R-caranlactam are polymerized in step i) of the process, preferably by ring-opening anionic polymerization, ring-opening cationic polymerization, hydrolytic polymerization or polycondensation to give 3S-polycaranamide, 3R-polycaranamide or 3S/3R-co-polycaranamide.

The present invention also relates to a method for the production of 3S-polycaranamide, as well as to polyamides obtained by this method, wherein, in particular, the 3S-caranlactam obtained according to the invention is polymerized in stage i) of the process, preferably by ring-opening anionic polymerization, cationic polymerization with ring opening, hydrolytic polymerization or polycondensation to give 3S-polycaranamide.

Therefore, the present invention also relates to 3S-polycaranamide.

The present invention also relates to a process for the production of 3R-polycaranamide, as well as to polyamides obtained by this process, wherein in particular the 3R-caranlactam obtained according to the invention is polymerized in process step i), preferably by anionic ring-opening polymerization, cationic polymerization with ring opening, hydrolytic polymerization or polycondensation to give 3R-polycaranamide.

Therefore, the present invention also relates to 3R-polycaranamide.

The present invention also relates to a method for the production of 3S/3R-co-polycaranamide, as well as to polyamides obtained by this method, wherein the mixture of 3S- and 3R-caranlactam, in particular the mixture of 3S- and 3R-caranlactam obtained according to the invention, is polymerized in the step i) a process, preferably by anionic ring-opening polymerization, cationic ring-opening polymerization, hydrolytic polymerization or polycondensation to form 3S/3R-co-polycaranamide.

Therefore, the present invention also relates to 3S/3R-co-polycaranamide.

The present invention also relates to a method for the production of co-polyamides, as well as co-polyamides obtained by this method, wherein the 3S-caranlactam, 3R-caranlactam or a mixture of 3S- and 3R-caranlactam obtained according to the invention and a monomer such as laurinlactam or caprolactam polymerized in step i2) of the process, preferably by ring-opening anionic polymerization, ring-opening cationic polymerization, hydrolytic polymerization or polycondensation to produce a co-polyamide, in particular 3S-caranlactam-laurinlactam-co-polycaranamide (3S-caranlactam- laurinlactam-co-polycaranamide), 3R-karanlactam-laurinlactam-co-polycaranamide (3R-karanlactam-laurinlactam-co-polycaranamide), 3S-karanlactam-3R-karanlactam-laurinlactam-co-polycaranamide (3S-karanlactam-3R-karanlactam- laurinlactam-co-polycaranamide), 3S-caranlactam-caprolactam-co-polycaranamide (3S-caranlactam-caprolactam-co-polycaranamide), 3R-caranlactam-caprolactam-co-polycaranamide (3R-caranlactam-caprolactam-co-polycaranamide) or 3S -karanlactam-3R-karanlactam-caprolactam-co-polycaranamide (3S-karanlactam-3R-karanlactam-caprolactam-co-polycaranamide).

The present invention also relates to a process for the production of polymers, in particular polyamides, which consist wholly of or contain, as a copolymer or part of a mixture, various polymers or monomers of the 3-caranlactams according to the invention, in particular 3S-polycaranamide and/or 3R-polycaranamide, in in particular 3S-polycaranamide or open amino acids, amino acid esters or amino acid derivatives thereof.

The present invention also relates to a process for the production of 3S-caranlactam from 3-carene, wherein the process comprises steps a) to c), e), f) and g), in particular a1) to c), e), f) and g), while in process step a) the 3S-caranepoxide obtained, preferably by epoxidation of 3-carene, is used, in process step c) a mixture enriched in 3S-caranone is obtained with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% of the 3S-caranone (relative to the total amount of caranone), in process step e) is converted into a mixture enriched in 3S-caranoxime with an isomer ratio of at least , 80%, in particular at least 85%, at least 90% or at least 95% of 3S-caranoxime (relative to the total amount of caranoxime), in process step f) is converted into a mixture enriched in 3S-caranlactam with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% of 3S-caranlactam (relative to the total amount of caranlactam), and in step g) 3S-caranlactam is obtained by crystallization.

In a preferred embodiment of the invention, in step ia) the 3S-caranlactam is then polymerized, preferably by anionic ring-opening polymerization, cationic ring-opening polymerization, hydrolytic polymerization or polycondensation, to obtain 3S-polycaranamide.

The present invention also relates to a process for the production of 3R-caranlactam from 3-carene, wherein the process comprises steps a) to c), e), f) and g), in particular a1) to c), e), f) and g), while in process step a) a 3R-caranepoxide obtained, preferably by epoxidation of 3-carene, is used, in process step c) a mixture enriched in 3R-caranone is obtained with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% of the 3R-caranone (relative to the total amount of caranone), in process step e) is converted into a mixture enriched in 3R-caranoxime with an isomer ratio of at least , 80%, in particular at least 85%, at least 90% or at least 95% of 3R-caranoxime (relative to the total amount of caranoxime), in step f) of the process is converted into a mixture enriched in 3R-caranlactam with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% of 3R-caranlactam (relative to the total amount of caranlactam), and after separation of 3S- caranlactam in step h) 3R-caranlactam is obtained.

In a preferred embodiment, in step ib), 3R-polycaranamide is then obtained from 3R-caranlactam by polymerization, preferably by anionic ring-opening polymerization, cationic ring-opening polymerization, hydrolytic polymerization or polycondensation.

The present invention also relates to a process for the production of 3R-caranlactam from 3-carene, wherein the process comprises steps a) to h), preferably a1) to h), wherein step a) of the process uses the product obtained, preferably by epoxidation, 3-carene 3S-caranepoxide, in process step c) a mixture enriched in 3S-caranone is obtained with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least , 95% 3S-caranone (relative to the total amount of caranone), it is isomerized in step d) of the process into a mixture enriched in 3R-caranone with an isomer content of at least 50%, in particular at least 60%, in particular at least 70%, in particular at least 80%, in particular at least 85%, in particular at least 90% or in particular at least 95% 3R-caranone (relative to the total amount of caranone), in step e) of the process, the mixture is converted into a mixture enriched in 3R-caranoxime with an isomer ratio of at least 50%, in particular at least 60%, in particular at least 70%, in particular at least 80%, in particular at least 85%, in particular at least 90% or in particular at least 95% 3R-caranoxime (relative to the total amount of caranoxime), in step f) of the process, the mixture is converted into a 3R-caranlactam enriched mixture with an isomer ratio of at least 50%, in particular at least 60%, in particular at least 70%, in particular at least 80%, in particular at least 85%, in particular at least 90% or in particular at least 95% of 3R-caranlactam (relative to the total amount of caranlactam) and after separation of 3S-caranlactam in the step h) the method to obtain 3R-canarlactam.

In a preferred embodiment, in step ib), 3R-polycaranamide is then obtained from 3R-caranlactam by polymerization, preferably by anionic ring-opening polymerization, cationic ring-opening polymerization, hydrolytic polymerization or polycondensation.

The present invention also relates to 3S-caranone, in particular, obtained or obtained by one of the methods of the present invention, corresponding to the formula:

The present invention also relates to 3S-caranoxime, in particular, obtained or obtained by one of the methods of the present invention, corresponding to the formula:

The present invention also relates to 3S-caranlactam, in particular, obtained or obtained by one of the methods of the present invention, corresponding to the formula:

In the context of the present invention, the number n is understood to be a natural number, in particular a natural number greater than or equal to 2, preferably a natural number between 2 and 1,000,000, in particular a natural number between 10 and 10,000, particularly preferably a natural number between 75 and 2000 , in particular, from 100 to 1000.

In the context of the present invention, the numbers a, b and c, in particular a and b, are understood in each case to be a natural number, in particular a natural number greater than or equal to 1, preferably a natural number between 1 and 1000, in particular natural number from 10 to 50.

In the context of the present invention, the number a is understood to mean a natural number, in particular a natural number greater than or equal to 1, preferably a natural number between 1 and 1000, particularly preferably a natural number between 10 and 50.

In the context of the present invention, the number b is understood to be a natural number, in particular a natural number greater than or equal to 1, preferably a natural number between 1 and 1000, particularly preferably a natural number between 10 and 50.

In the context of the present invention, c is understood to mean a natural number, in particular a natural number greater than or equal to 1, preferably a natural number between 1 and 1000, particularly preferably a natural number between 10 and 50.

In the context of the present invention, the natural numbers a and b have a ratio preferably between 1:100 and 100:1, preferably between 1:10 and 10:1, particularly preferably between 1:6 and 6:1.

In the context of the present invention, the natural numbers a and c have a ratio preferably between 1:100 and 100:1, preferably between 1:10 and 10:1, particularly preferably between 1:6 and 6:1.

In the context of the present invention, the natural numbers b and c have a ratio preferably between 1:100 and 100:1, preferably between 1:10 and 10:1, particularly preferably between 1:6 and 6:1.

In a preferred embodiment of the invention, the natural numbers n, a, b and c, in particular a, b and c, in particular a and b, are the same or different from each other. In a preferred embodiment of the present invention, the natural numbers n, a, b and c are independent of each other.

The present invention also relates to 3S-polycaranamide, in particular, obtained or obtained by one of the methods of the present invention, corresponding to the formula (with n repeating units):

In a preferred embodiment of the invention, it is provided that the 3S-polycaranamide according to the invention consists only of repeating 3S-polycaranamide units of the following formula:

It is also preferably provided that the 3S-polcaranamide according to the invention comprises at least 80%, in particular at least 85%, in particular at least 90%, in particular at least 95% , in particular at least 98%, in particular at least 99%, in particular at least 99.5%, in particular at least 99.9%, in particular 100% (relative to the total number n of repeating units) repeating units of 3S-polycaranamide of the following formula:

The present invention also relates to 3R-polycaranamide, in particular, obtained or obtained by one of the methods of the present invention, corresponding to the formula (with n repeating units):

In a preferred embodiment of the invention, it is provided that the 3R-polycaranamide according to the invention consists only of repeating 3R-polycaranamide units of the following formula:

It is also preferably provided that the 3R-polcaranamide according to the invention comprises at least 80%, in particular at least 85%, in particular at least 90%, in particular at least 95% , in particular at least 98%, in particular at least 99%, in particular at least 99.5%, in particular at least 99.9%, in particular 100% (relative to the total number n of repeating units) repeating units of 3R-polycaranamide of the following formula:

The present invention also relates to a co-polycaranamide obtained or obtained by one of the methods of the present invention, in particular from 3S-caranlactam, 3R-caranlactam or a mixture of 3S-caranlactam and 3R-caranlactam, containing at least one repeating unit of the following formula :

and at least one repeating unit of the following formula:

The present invention also relates to 3S/3R-co-polycaranamide, in particular, obtained or obtained by one of the methods of the present invention, corresponding to the formula (with a, b and n repeating units):

The present invention also relates to a co-polycaranamide obtained or obtained by one of the methods of the present invention, in particular from 3S-caranlactam, 3R-caranlactam or a mixture of 3S-caranlactam and 3R-caranlactam, containing at least one other lactam, when in this case, the co-polycaranamide includes at least one built-in lactam, preferably laurin lactam and/or caprolactam, and at least one repeating unit of the formula:

or at least one repeating unit of the formula:

or both of these repeating links.

The present invention also relates to co-polycaranamide obtained or obtained by one of the methods of the present invention, in particular from 3S-caranlactam, 3R-caranlactam or a mixture of 3S-caranlactam and 3R-caranlactam, with at least one additional lactam, in particular , containing at least one of the following repeating units corresponding to one of the following formulas (with a, b and c repeating units):

in this case, A refers to a repeating unit of an additional lactam built into the co-polyamide.

Preferably, it is contemplated that the lactam is selected from the group consisting of laurin lactam, caprolactam and a mixture of said lactams.

The present invention also relates to a co-polycaranamide obtained or obtained by one of the methods of the present invention, in particular from 3S-caranlactam or a mixture of 3S-caranlactam and 3R-caranlactam, with at least one additional lactam, in particular containing, at least one of the following repeating units corresponding to one of the following formulas (with a, b and c repeating units):

,

in this case, A refers to a repeating unit of an additional lactam built into the co-polyamide.

Preferably, it is contemplated that the lactam is selected from the group consisting of laurin lactam, caprolactam and a mixture of said lactams.

The present invention also relates to a co-polycaranamide obtained or obtained by one of the methods of the present invention, in particular from 3R-caranlactam or a mixture of 3S-caranlactam and 3R-caranlactam, with at least one additional lactam, in particular containing, at least one of the following repeating units corresponding to one of the following formulas (with a, b and c repeating units):

,

in this case, A refers to a repeating unit of an additional lactam built into the co-polyamide.

Preferably, it is contemplated that the lactam is selected from the group consisting of laurin lactam, caprolactam and a mixture of said lactams.

The present invention also relates to 3S-caranlactam-laurinlactam-co-polycaranamide (3S-caranlactam-laurinlactam-co-polycaranamide), in particular obtained or obtained by one of the methods of the present invention, in particular from 3S-caranlactam and laurinlactam in particular, corresponding formula (with a, b and n repeating links):

The present invention also relates to 3S-caranlactam-caprolactam-co-polycaranamide (3S-caranlactam-caprolactam-co-polycaranamide), in particular obtained or obtained by one of the methods of the present invention, in particular from 3S-caranlactam and caprolactam in particular, corresponding formula (with a, b and n repeating links):

The present invention also relates to 3R-caranlactam-laurinlactam-co-polycaranamide (3R-caranlactam-laurinlactam-co-polycaranamide), in particular obtained or obtained by one of the methods of the present invention, in particular from 3R-caranlactam and laurinlactam in particular, corresponding formula (with a, b and n repeating links):

.

The present invention also relates to 3R-caranlactam-caprolactam-co-polycaranamide (3R-caranlactam-caprolactam-co-polycaranamide), in particular obtained or obtained by one of the methods of the present invention, in particular from 3R-caranlactam and caprolactam in particular, corresponding formula (with a, b and n repeating links):

The present invention also relates to 3S-caranlactam-3R-caranlactam-laurinlactam-co-polycaranamide (3S-caranlactam-3R-caranlactam-laurinlactam-co-polycaranamide), in particular obtained or obtained by one of the methods of the present invention, in particular from 3S-caranlactam, 3R-caranlactam and laurinlactam, in particular corresponding to the formula (with a, b, c and n repeating units):

The present invention also relates to 3S-caranlactam-3R-caranlactam-caprolactam-co-polycaranamide (3S-caranlactam-3R-caranlactam-caprolactam-co-polycaranamide), in particular obtained or obtained by one of the methods of the present invention, in particular from 3S-caranlactam, 3R-caranlactam and caprolactam, in particular corresponding to the formula (with a, b, c and n repeating units):

The present invention also relates to products, in particular plastic products, containing at least one of the polyamides produced according to the invention, in particular 3S-polycaranamide, 3R-polycaranamide, or at least one of the co- polycaranamides, in particular containing at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 30 wt% ., at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least , 90% wt., at least 95% wt. or at least 99 wt%. polyamide, in particular consisting of at least one of these polyamides.

In one of the preferred embodiments of the invention, such plastic products are industrial products, medical products or structural elements.

Disclosed in the context of the present invention, the preferred embodiments of steps a1) - i2) of the method for the production and subsequent conversion of an isomer-enriched mixture of 3S-caranone and 3R-caranone according to the invention are also preferred steps a1) - i2) of the method for the production of a mixture enriched with 3-caranoxime, 3-caranlactam enriched blend, 3S-polycaranamide, 3R-polycaranamide, 3S/3R-co-polycaranamide, 3S-caranlactam-laurinlactam-co-polycaranamide (3S-caranlactam-laurinlactam-co-polyamide), 3R-caranlactam-laurinlactam-co -polycaranamide (3R-karanlactam-laurinlactam-co-polyamide), 3S-karanlactam-3R-karanlactam-laurinlactam-co-polycaranamide (3S-karanlactam-3R-karanlactam-laurinlactam-co-polyamide), 3S-karanlactam-caprolactam-co -polycaranamide (3S-karanlactam-caprolactam-co-polyamide), 3R-karanlactam-caprolactam-co-polycaranamide (3R-karanlactam-caprolactam-co-polyamide), 3S-caranthactam-3R-karanlactam-caprolactam-co-polycaranamide (3S -karanlactam-3R-karanlactam-caprolactam-co-polyamide), as well as 3S-caranoxime, 3S-karanlactam, 3S-polycaranamide, 3R-polycaranamide, 3S/3R-co-polycaranamide, 3S-karanlactam-laurinlactam-co-polycaranamide ( 3S-karanlactam-laurinlactam-co-polyamide), 3R-karanlactam-laurinlactam-co-polycaranamide (3R-karanlactam-laurinlactam-co-polyamide), 3S-karanlactam-3R-karanlactam-laurinlactam-co-polycaranamide (3S-karanlactam- 3R-karanlactam-laurinlactam-co-polyamide), 3S-karanlactam-caprolactam-co-polycaranamide (3S-karanlactam-caprolactam-co-polyamide), 3R-karanlactam-caprolactam-co-polycaranamide (3R-karanlactam-caprolactam-co- polyamide), as well as 3S-caranlactam-3R-caranlactam-caprolactam-co-polycaranamide (3S-caranlactam-3R-caranlactam-caprolactam-co-polyamide) and polymers, in particular polyamides, which consist entirely of or contain as a copolymer or parts of a mixture of various polymers or monomers of 3-caranlactams or open amino acids, amino acid esters or amino acid derivatives thereof.

The invention also relates to polymers, in particular polyamides, which consist wholly of or contain, as a copolymer or part of a mixture, various polymers or monomers of the 3-caranlactams according to the invention, in particular 3S-caranlactam or 3R-caranlactam, in particular 3S-caranlactam or their open-ended amino acids, amino acid esters or amino acid derivatives, preferably according to the above formulas 3S-caranlactam, 3S-polycaranamide, 3R-polycananamide and 3S/3R-co-polycaranamide.

Other preferred embodiments of the invention appear in particular from the dependent claims.

The following examples and their corresponding figures explain the present invention.

The figures show:

Figure Description Fig. 1 Overview of steps a1) - f) of the method Fig. 2 Overview of steps i) and i2) of the method Fig. 3 GC-chromatogram of a mixture of isomers enriched in 3S-caranone Fig. 4 GC-chromatogram of a mixture of isomers enriched in 3R-caranone Fig. 5 1H-NMR of 3S-caranone Fig. 6 13C-NMR of 3S-caranone Fig. 7 1H-NMR 3S-caranoxime Fig. 8 13C-NMR 3S-caranoxime Fig. 9 1H-NMR of 3S-caranlactam Fig. 10 13C-NMR of 3S-caranlactam Fig. eleven 1H-NMR spectrum of 3S-polycaranamide Fig. 12 13C-NMR spectrum of 3S-polycaranamide Fig. 13 Spectrum of COZY 3S-polycaranamide Fig. 14 HSQC spectrum of 3S-polycaranamide Fig. 15 Spectrum of DEPT 3S-polycaranamide Fig. 16 1H-NMR spectrum of 3R-polycaranamide Fig. 17 13C-NMR spectrum of 3R-polycaranamide Fig. 18 Spectrum of COZY 3R-polycaranamide Fig. 19 HSQC spectrum of 3R-polycaranamide Fig. 20 Spectrum of DEPT 3R-polycaranamide Fig. 21 1H-NMR spectrum of 3S-caranlactam-3R-caranlactam-co-polycaranamide Fig. 22 13C-NMR spectrum of 3S-karanlactam-3R-karanlactam-co-polycaranamide Fig. 23 1H-NMR spectrum of 3S-caranlactam-laurinlactam-co-polycaranamide Fig. 24 1H-NMR spectrum of 3S-caranlactam-caprolactam-co-polycaranamide Fig. 25 DSC curve of 3S-polycaranamide Fig. 26 DSC curve of 3S-polycaranamide Fig. 27 DSC curve of 3S-polycaranamide Fig. 28 DSC curve of 3S-polycaranamide Fig. 29 DSC curve of 3S-polycaranamide Fig. thirty DSC curve of 3S-polycaranamide Fig. 31 DSC curve of 3S-polycaranamide Fig. 32 DSC curve of 3S-polycaranamide Fig. 33 DSC curve of 3S-polycaranamide Fig. 34 DSC curve of 3S-polycaranamide Fig. 35 DSC curve of 3R-polycaranamide Fig. 36 DSC curve of 3R-polycaranamide Fig. 37 DSC curve of 3R-polycaranamide Fig. 38 DSC curve of 3R-polycaranamide Fig. 39 DSC curve of 3R-polycaranamide Fig. 40 DSC curve of 3R-polycaranamide Fig. 41 DSC curve of 3R-polycaranamide Fig. 42 DSC curve of 3R-polycaranamide Fig. 43 DSC curve of 3S-caranlactam-3R-caranlactam-co-polycaranamide Fig. 44 DSC curve of 3S-caranlactam-3R-caranlactam-co-polycaranamide Fig. 45 DSC curve of 3S-caranlactam-laurinlactam-co-polycaranamide Fig. 46 DSC curve of 3S-caranlactam-laurinlactam-co-polycaranamide Fig. 47 DSC curve of 3S-caranlactam-laurinlactam-co-polycaranamide Fig. 48 DSC curve of 3S-caranlactam-caprolactam-co-polycaranamide Fig. 49 DSC curve of 3S-caranlactam-caprolactam-co-polycaranamide Fig. 50 DSC curve of 3S-caranlactam-caprolactam-co-polycaranamide Fig. 51 3S-polycaranamide GPC curve Fig. 52 3S-polycaranamide GPC curve Fig. 53 3S-polycaranamide GPC curve Fig. 54 3S-polycaranamide GPC curve Fig. 55 3S-polycaranamide GPC curve Fig. 56 3S-polycaranamide GPC curve Fig. 57 3S-polycaranamide GPC curve Fig. 58 3S-polycaranamide GPC curve Fig. 59 3S-polycaranamide GPC curve Fig. 60 3S-polycaranamide GPC curve Fig. 61 3S-polycaranamide GPC curve Fig. 62 3R-polycaranamide GPC curve Fig. 63 3R-polycaranamide GPC curve Fig. 64 3R-polycaranamide GPC curve Fig. 65 3R-polycaranamide GPC curve Fig. 66 3R-polycaranamide GPC curve Fig. 67 3R-polycaranamide GPC curve Fig. 68 3R-polycaranamide GPC curve Fig. 69 3R-polycaranamide GPC curve Fig. 70 3R-polycaranamide GPC curve Fig. 71 3R-polycaranamide GPC curve Fig. 72 3S-caranlactam-3R-caranlactam-polycaranamide GPC curve Fig. 73 3S-caranlactam-laurinlactam-co-polycaranamide GPC curve Fig. 74 3S-caranlactam-laurinlactam-co-polycaranamide GPC curve Fig. 75 3S-caranlactam-laurinlactam-co-polycaranamide GPC curve Fig. 76 GPC curve of 3S-caranlactam-caprolactam-co-polycaranamide Fig. 77 GPC curve of 3S-caranlactam-caprolactam-co-polycaranamide Fig. 78 3S-polycaranamide GPC curve Fig. 79 3R-polycaranamide GPC curve Fig. 80 GPC curve of 3S-caranlactam-caprolactam-co-polycaranamide Fig. 81 DSC curve of 3S-polycaranamide Fig. 82 DSC curve of 3R-polycaranamide Fig. 83 DSC curve of 3S-caranlactam-3Rcaranlactam-co-polycaranamide

COZY - two-dimensional correlation spectroscopy

DEPT - Distortionless Enhancement by Polarization Transfer

DSC - Differential Scanning Calorimetry

GPC - Gel Permeation Chromatography

HSQC - Heteronuclear Single Quantum Coherence spectroscopy

Analytical Methods

Analytical GCMS Method (1) (Gas Chromatography/Mass Spectrometry)

Studies of the reaction mixture by gas chromatographic separation followed by mass spectrometric analysis

Gas chromatographic analysis was performed on a GC-2010 Plus (Shimadzu), separation was performed on a capillary column (BPX 5: 5% phenyl, 95% methylpolysilphenylene/siloxane, SGE). MS-QP2010 Plus (Shimadzu) with electroionization (70 eV) was used for mass spectrometric analysis. GC-MS Postrun Analysis (Shimadzu) was used as software for data analysis. The obtained data were compared with the databank (Datenbank Version 08) of the National Institute of Standards and Technology (National Institute of Standards and Technology).

Table 2: Gas chromatographic analysis parameters

Parameter Value Split ratio 5 Injection temperature 250°C carrier gas Helium Volumetric flow in the column 1.69 ml/min Heating program 50°C/min 50-120°C, heating 15°C/min 120-170°C, heating 15°C/min 170-200°C, heating 15°C/min 200°C, 7 min Column BPX5 ( CS Chromatography ) length 30 m, inner diameter 0.25 µm, diameter 0.25 mm

An exemplary chromatogram of a 3S-caranone enriched mixture (FIG. 3) and a 3R-caranone enriched mixture (FIG. 4) are shown in the figures.

Table 3 below lists the retention times for all related products.

Table 3: Retention times

Compound Retention time, min 3-karen 5.69 3S-caranepoxide 7.25 3S-caranon 8.15 3R-caranon 8.04 3R-caranoxime (trans) 11.11 3S-caranoxime (trans) 10.75 3S-karanlactam 14.61 3R-caranlactam 14.14

The percentage of 3S-caranone and 3R-caranone in an isomer-enriched mixture can be determined from a comparison (product peak area divided by the total peak area of the two products) of the peak areas, in particular the TIC (total ion current) peak areas of the products 3S-caranone and 3R-caranone with retention times according to the table "Retention times of all compounds related to the products". Assuming, without being bound by any theory, that both 3S-caranone and 3R-caranone products decompose into the same number of fragments and therefore excite the corresponding ion current, the peak area ratio calculated from the above data also corresponds to the ratio of 3S products -caranon and 3R-caranon. The procedure performed here for the isomer-enriched mixture of 3S-caranone and 3R-caranone is also valid for the mixture enriched in 3-caranoxime and the mixture enriched in 3-caranlactam.

Analytical NMR Method (2) (Nuclear Magnetic Resonance)

Study of the reaction mixture by NMR spectroscopy

NMR measurements were performed on a JEOL JNM-ECA 400 MHz spectrometer using the JEOL Delta v5.0.4 software at 25°C using the Standard-Pulse program included with JEOL Delta v5.0.4. The DEPT135° technique was used to identify CH2 signals. If necessary, 2D NMR methods (COSY, HSQC, HMBC) were used. The polymers were measured in DCOOD, all other compounds in DMSO-d6. The measurement results were processed using the JEOL Delta v5.0.4 software.

NMR spectra (1H, 13C) of the compounds 3S-caranone (1H: Fig. 5, 13C: Fig. 6), 3S-caranoxime (1H: Fig. 7, 13C: Fig. 8) and 3S-caranlactam (1H: Fig. 9, 13C: Fig. 10), as well as 3S-polycaranamide polymers (1H: Fig. 11, 13C: Fig. 12, COZY: Fig. 13, HSQC: Fig. 14, DEPT: Fig. 15), 3R-polycaranamide (1H: Fig. 16, 13C: Fig. 17, COZY: Fig. 18, HSQC: Fig. 19, DEPT: Fig. 20) and 3S/3R-co-polycaranamide (1H: Fig. 21, 13C: Fig. 22), 3S-caranlactam-laurinlactam-co-polycaranamide (1H: FIG. 23) and 3S-caranlactam-caprolactam-co-polycaranamide (1H: FIG. 24) are shown in their respective figures.

Analytical DSC Method (3) (Differential Scanning Calorimetry)

DSC analysis was performed on a DSC-One from Mettler Toledo. The measurement results were processed using the STARe software (version: 13.00a (Build6917) manufactured by Mettler Toledo:

Table 4: DSC analysis parameters

c Value Shielding gas nitrogen Heating I -20°C to 350°C Heating rate I 20K/min Cooling I 350°C to -20°C Cooling rate I -20K/min Heating II
Heating rate II
Sample weight -20°C to 350°C
10K/min
5 mg to 10 mg

The DSC spectra of the polymers 3S-polycaranamide (FIG. 81), 3R-polycaranamide (FIG. 82), and 3S/3R-co-polycaranamide (FIG. 83) are presented in the corresponding figures and reflect the heating process II.

DSC analytical method, method (3.1) (Differential Scanning Calorimetry)

DSC analysis according to method (3.1) was performed on a DSC-One instrument manufactured by Mettler Toledo with software STARe V. 13.00. Samples (5-10 mg) were measured in an aluminum crucible under a nitrogen atmosphere. Method (3.1) was used for the analysis of 3S-polycaranamide. The respective figures 35-50 show segment 10.

Table 4.1: Parameters of DSC analysis by method (3.1)

Segment Temperature, °C
start/end Heating rate, K/min N ₂ ml/min 1 -20°C, 2 min isothermal 50 2 -20°C/320°C 10 50 3 320°C, 1 min isothermal 50 4 320°C/-20°C -10 50 5 -20°C, 1 min isothermal 50 6 -20°C/320°C 10 50 7 320°C, 1 min isothermal 50 8 320°C/-20°C -10 50 9 -20°C, 1 min isothermal 10 -20°C/320°C 10

The DSC spectra of 3S-polycaranamide (FIGS. 25 to 34 inclusive) are shown in the respective figures.

DSC analytical method, method (3.2) (Differential Scanning Calorimetry)

DSC analysis according to method (3.2) was performed on a DSC-One instrument manufactured by Mettler Toledo with software STARe V. 13.00. Samples (5-10 mg) were measured in an aluminum crucible under a nitrogen atmosphere. Method (3.2) was used to analyze 3R-polycaranamide, 3S-caranlactam-3R-caranlactam-co-polycaranamide, 3S-caranlactam-laurinlactam-co-polyamide, and 3S-caranlactam-caprolactam-co-polyamide. The respective figures 35-50 show segments 6 and 7.

Table 4.2: Parameters of DSC analysis by method (3.2)

Segment Temperature, °C
start/end Heating rate, K/min N ₂ ml/min 1 20/350 20 50 2 350/20 -20 50 3 20/220 10 50 4 220 (20 min) isothermal 50 5 220/0 -10 50 6 0/370 10 50 7 370/0 -10 50 8 0/440 10 50

DSC spectra of 3R-polycaranamide (Fig. 35 to 42 inclusive), as well as 3S/3R-co-polycaranamide (Fig. 43 and Fig. 44), 3S-caranlactam-laurinlactam-co-polycaranamide (Fig. 45, Fig. 46 , Fig. 47) and 3S-caranlactam-caprolactam-co-polycaranamide (Fig. 48, Fig. 49, Fig. 50) are presented in the respective figures.

Analytical GPC Method (4.1) (Gel Permeation Chromatography)

GPC measurements were performed on an Agilent 1200 Series manufactured by Agilent with PMMA calibration. The measurement results were processed using the ChemStation GPC software (WINGPC Unity, Build 5403).

Table 5.1: Parameters of GPC analysis by method (4.1)

Parameter Value Column HFIP Gel column eluent HFIP Temperature 40°C Injection volume 20 µl Consumption 0.5 ml/min Concentration 1 g/l

The GPC spectra of 3S-polycaranamide (FIG. 78), 3R-polycaranamide (FIG. 79), and 3S-caranlactam-caprolactam-co-polycaranamide (FIG. 80) polymers are shown in the respective figures.

Analytical GPC Method (4.2) (Gel Permeation Chromatography)

GPC measurements were performed on a SECurity GPC with an autosampler (1260 Infinity, Agilent Technologies) and a TCC6000 column oven (Polymer Standard Services, PSS). Data were processed using PSS WinGPC UniChrom (PSS). PMMA standards were used to calibrate the molar mass. For coarse calibration, PA6 standards were used (PSS ready-call-kit, M _w /M _n = 31400/17400 Da; 22000/13000 Da; 17200/11300 Da). The lower molecular weight limit for processing was set to 1.0 kDa.

Table 5.2: Parameters of GPC analysis by method (4.2)

parameter Value Column temperature 35C Consumption 0.6 ml/min eluent 0.05M NaTFA in HFIP Sample concentration 1.0 mg/ml Injection volume 50 µl Elution time 30 min Elution volume 18.6 ml Column 1 PSS PFG forecolumn Column 2 PSS PFG 100Å Column 3 PSS PFG 1000Å

GPC spectra of polymers 3S-polycaranamide (Fig. 51 to Fig. 61 inclusive), 3R-polycaranamide (Fig. 62 to Fig. 71 inclusive), 3S/3R-co-polycaranamide (Fig. 72), 3S-caranlactam-laurinlactam- co-polycaranamide (Fig. 73, Fig. 74 and Fig. 75), as well as 3S-caranlactam-caprolactam-co-polycaranamide (Fig. 76 and Fig. 77) are presented in the respective figures.

Determination of water absorption in qualitative comparison with PA6, method (5)

PA6 was prepared by ring-opening anionic polymerization (2.8 mmol caprolactam, 0.1 mmol 60% NaH on paraffin wax, 0.05 mmol Ac ₂ O, 180° C.). The rest of the monomer was removed by boiling under reflux in water/ethanol. 30-42 mg of PA6 (three samples) and at least two samples of the polyamide according to the invention were kept for three minutes at 230°C in a DSC (same apparatus as described in relation to the DSC method (3)) and thus obtained uniform polyamide blocks. Weight was determined using an OHAUS Discovery DV215CD balance with a maximum error of 0.01 mg. The samples were then, in each case, stirred for three days in water at 25°C. The samples were then air dried and weighed after 30 minutes and four and a half hours. Finally, the samples were dried for three hours at 80°C and weighed. Qualitatively, compared to PA6, water absorption can be assessed by comparing the masses after the water bath with the reduction in mass after the drying steps.

Determination of transparency in qualitative comparison with PA6 and PA12, method (6)

PA6 and PA12 were dissolved in HFIP (25 mg/ml) and transferred to laboratory crystallizers (diameter 4 to 12 cm) or applied to PTFE film. After evaporation of the solvent, it was dried at 85° C. for at least three hours. White, opaque films were obtained and the transparency of the polymers according to the invention was determined by visual comparison.

EXAMPLES OF CARRYING OUT THE INVENTION

Example 1 (process steps a), b) and c): synthesis of 3S-caranone (isomer purity greater than 85%)

1.8 g of 3S-caranepoxide (11.8 mmol) was dissolved in 6.7 ml of hexane (c=1.5 M) and heated to 60°C. 7.0 mg Fe(ClO ₄ ) ₂ ·H ₂ O (0.03 mmol, 0.2 mol %) was added and stirred for 20 minutes. The reaction mixture was cooled to 25° C. and 2 ml of half-saturated sodium acetate solution was added. The phases were separated, the solvent was removed by distillation.

GCMS analysis (uncorrected): overall selectivity 80% caranone, ratio 3S-caranone/3R-caranone 85%:15%.

Mass spectrum:

MS (EI (electron ionization), 70 eV): m/z (mass-to-charge ratio) (%) = 153.10 (2.77), 152.10 (27.38), 138.10 (1.16), 137.10 (12.12), 135.15 (0.47), 134.10 (2.59), 125.15 (0.48), 124.10 (4.38), 123.10 (4.10), 121.10 (0.54).

MS (EI, 70 eV): % (m/z) = 100.00 (67.10), 83.36 (81.10), 69.63 (41.10), 45.24 (39.10), 44.25 (82.10), 33.71 (95.10), 32.68 (109.10), 30.74 (110.10), 27.40 (55.10), 27.38 (152.10).

In FIG. 4 is a GC chromatogram of a mixture of isomers enriched in 3S caranone.

In FIG. 5 shows the 1H-NMR spectrum of 3S-caranone (in pure form), FIG. 6 shows the 13C-NMR spectrum of 3S-caranone (in pure form).

Interpretation of the NMR spectrum

¹ H NMR (400 MHz, DMSO-d6): δ/ppm=2.56-2.47 (m, 1H, -CO-C H ₂ -CH-, solvent overlay), 2.10 (qdd, J=7.3, 5.0, 2.7 Hz, 1H, -C H CH ₃ -), 2.03-1.90 (m, 2H, -CHCH ₃ -C H ₂ -CH-, -CO-C H ₂ -CH-), 1.70-1.62 (m, 1H, -CHCH ₃ -C H ₂ -CH-), 1.13 (d, J=7.2 Hz, 3H, -CHC H ₃ -), 1.04 (s, 3H, -CCHC H ₃ CH ₃ -), 1.03-0.97 (m , 1H, -CO-CH ₂ -C H -), 0.90 (s, 3H, -CCHCH ₃ C H ₃ -), 0.80 (td, J=8.9, 6.4 Hz, 1H, -CHCH ₃ -CH ₂ -C H- ).

¹³ C NMR (100 MHz, DMSO-d6): δ/ppm=216.1 (- C O-), 40.7 (- C HCH ₃ -), 33.9 (-CO- C H ₂ -CH-), 27.8 (-CCHCH C H ₃ CH ₃ -, 26.3 (-CHCH ₃ - C H ₂ -CH-), 21.1 (-CO-CH ₂ - C H-), 19.0 (- C CHCHCH ₃ CH ₃ -), 16.7 (-CH C H ₃ -), 16.4 (-CO-CH ₂ -CH- ), 14.6 (-CCHCHCH ₃ C H ₃ -).

Example 1.1: Proper solvent

Table 6: Effect of solvent polarity on the isomerization of 3S-caranepoxide to give a mixture enriched in 3S-caranone and 3R-caranone. All experiments were carried out with a concentration of 3S-caranepoxide 1M at 25°C and 0.2% mol. Fe(ClO ₄ ) ₂ ·H ₂ O 8 h. The degree of conversion of 3S-caranepoxide was 100%. These values also refer to the area of the TIC peaks of the GCMS spectra (uncorrected)

Solvent Relative polarity* Karanon, % 3R-Karanon, % 3S-Karanon, % 1 Cyclohexane 0.006 70 eleven 89 2 Hexane 0.009 64 13 87 3 Toluene 0.099 71 14 86 4 Heptane 0.012 64 13 87 *Source: Christian Reichardt, Solvents and Solvent Effects in Organic Chemistry, Wiley-VCH Publishers, 3rd Ed., 2003

Example 1.2.1: Comparison of Lewis acids with zinc ion and iron ion

Table 7: Comparison of Fe- and Zn-Lewis acids at 60° C. in cyclohexane at a concentration of 1M 3S-caranepoxide and 0.2 mol %. catalyst. These values also refer to the area of the TIC peaks of the GCMS spectra (uncorrected)

Catalyst [0.2%] Degree of conversion, % Karanon, % 3R-Karanon, % 3S-Karanon, % t, h 1 Zn(OTf) ₂ 48 70 9 91 40 2 Fe(OTf) ₂ 91 73 15 85 0.5 3 Fe(ClO ₄ ) ₂ ∙H ₂ O 100 82 15 85 0.5 4 Fe(ClO ₄ ) ₃ ∙H ₂ O 100 81 16 84 0.5

Example 1.2.2: Comparison of different sulfonic acids

Table 8: Conversion by Meinwald isomerization of 3S-caranepoxide to a mixture enriched in 3S-caranone and 3R-caranones using various sulfonic acids as acid catalyst. The values in Table 4 also refer to the area of the TIC peaks of the GCMS spectra (uncorrected)

Catalyst [%] Solvent c, M T, °C Degree of conversion, % Karanon, % 3R-Karanon, % 3S-Karanon, % t, h 1 _{CF3SO3H 0.1} % Toluene 1 25 100 73 13 87 12 2 PTSA 1% Cyclohexane 1 60 100 69 17 83 12

Example 1.3 Proper Lewis Acid Concentrations

Table 9: Effect of the amount of Fe(ClO ₄ ) ₂ ·H ₂ O on the conversion to the 3R- and 3S-caranone isomers. All experiments were performed at a concentration of 1M 3S-caranepoxide at 25°C for 5 hours. These values also refer to the area of the TIC peaks of the GCMS spectra (without correction). All experiments were carried out in cyclohexane

Fe(ClO ₄ ) ₂ ∙H ₂ O, mol %. Degree of conversion, % Karanon, % 3R-Karanon, % 3S-Karanon, % 1 0.1 90 71 20 80 2 0.25 95 69 14 86 3 0.5 98 67 15 85 4 1 100 63 15 85

Example 1.4 Proper Concentrations of 3S-Caranepoxide

Table 10: Effect of 3S-caranepoxide concentration on the conversion of 3S-caranepoxide to a mixture enriched in 3S-caranone and 3R-caranone. All experiments were carried out at 25°C and 0.2% Fe(ClO ₄ ) ₂ ·H ₂ O 7 h. These values also refer to the area of the peaks of the TIC spectra of GCMS (without correction). All experiments were carried out in cyclohexane

3S-caranepoxide, M Degree of conversion, % Karanon, % 3R-Karanon, % 3S-Karanon, % 1 0.25 8 56 20 80 2 0.5 78 74 13 87 3 1.0 100 70 10 90 4 2.0 100 67 10 90 5 3.0 100 66 10 90

Example 1.5: Effect of temperature

Table 11: Influence of temperature using Lewis acids on Mainvaln isomerization of 3S-caranepoxide. These values also refer to the area of the TIC peaks of the GCMS spectra (uncorrected)

Catalyst [%] Solvent c, M T, °C Degree of conversion, % Karanon, % 3R-Karanon, % 3S-Karanon, % t 1 Fe(ClO ₄ ) ₂ ∙H ₂ O 0.2% Cyclohexane 1 25 100 70 10 90 7 h 2 Fe(ClO ₄ ) ₂ ∙H ₂ O 0.2% Cyclohexane 1 60 100 82 15 85 5 minutes

Example 1.6 Lewis acids without iron ion

15.2 mg of 3S-caranepoxide (0.1 mmol) was dissolved in 1 ml of toluene. Then added 2% mol. solution of Ni(ClO ₄ ) ₂ in ethyl acetate, the reaction mixture was heated for 20.5 h at 60°C. GCMS analysis (uncorrected): total purity of caranone 88.9%, 3S caranone 92.0% and 3R caranone 8.0%.

15.2 mg of 3S-caranepoxide (0.1 mmol) was dissolved in 1 ml of toluene. Then added 2% mol. solution of Co(ClO ₄ ) ₂ in ethyl acetate, the reaction mixture was heated for 20.5 h at 60°C. GCMS analysis (uncorrected): total purity of caranone 89.0%, 3S caranone 93.3% and 3R caranone 6.7%.

15.2 mg of 3S-caranepoxide (0.1 mmol) was dissolved in 1 ml of toluene. Then added 2% mol. solution of Cu(ClO ₄ ) ₂ in ethyl acetate, the reaction mixture was heated for 20 h at room temperature. GCMS analysis (uncorrected): total purity of caranone 63.0%, 3S caranone 85.0% and 3R caranone 15.0%.

Example 2.1 (process step d): Isomerization of 3S-caranone to 3R-caranone

152 µl of an approximately 80% solution enriched in 3S-caranone (87%) and 3R-caranone (13%) mixture of Example 1 was dissolved in 845 µl of MeCN and 5 µl of sulfuric acid was added. The reaction mixture was stirred for 5 h at 60°C. The solvent was separated by distillation.

GCMS analysis (uncorrected): overall selectivity 80% caranone, ratio 3S-caranone/3R-caranone 85%:15%. In FIG. 4 is a GC chromatogram of a mixture of isomers enriched in 3S caranone. In FIG. 5 shows the 1H-NMR spectrum of 3S-caranone (in pure form), FIG. 6 shows the 13C-NMR spectrum of 3S-caranone (in pure form).

Example 2.1 (process step d): Influence of the solvent on the isomerization of 3S-caranone to 3R-caranone (III)

Table 12: Effect of solvent on the isomerization of a 3S-caranone enriched mixture (purity 79%, 3S-caranone 89%, 3R-caranone 11%). All experiments were carried out at a concentration of 1M 3S-caranone with a 2M HCl solution as an isomerization catalyst. Samples were taken after 6 hours at room temperature (a), after another 15 hours at room temperature (b) and after another 48 hours of stirring at 60°C (c). These values also refer to the area of the TIC peaks of the GCMS spectra (uncorrected)

Solvent Relative polarity* Karanon, % 3R-Karanon, % 3S-Karanon, % (a) (b) (c) (a) (b) (c) (a) (b) (c) 1 Tetrahydrofuran 0.207 76 76 73 22 15 22 78 85 78 2 ethyl acetate 0.228 77 77 73 45 15 22 55 85 78 3 Acetone 0.355 78 78 thirty 15 15 0 85 85 100 4 Acetonitrile 0.460 78 78 20 20 18 0 80 82 100

Example 3.1 (process step a1a): Epoxidation of 3-carene using Cal-B lipase enzyme to produce 3S-caranepoxide (greater than 99%)

10.87 g of 3-carene (80 mmol) was dissolved in 160 ml of ethyl acetate and loaded into a reactor with a KPG stirrer and a nylon bag with 2.5 Cal-B lipase from Candida antarctica (immobilized). The reactor was heated to 60° C. and 9.35 g of H ₂ O ₂ (2 ml/h) was continuously added. After 4 hours, the reaction mixture was cooled to room temperature, the enzyme bag was removed, washed with 2 x 50 ml of 2M NaOH, 1 x 50 ml of a saturated solution of Na ₂ SO ₃ and 1 x 50 ml of water. The solvent was removed under reduced pressure.

GCMS analysis (uncorrected): 3S-caranepoxide (2) >99%.

Example 3.2 (process step a1a): Epoxidation of 3-carene with dilute peracetic acid to give 3S-caranepoxide (over 99%)

1 eq. NaOAc was dissolved in 12% peracetic acid to c=1M (respectively, 1.3 eq. peracetic acid) and 1 eq. 3-carena. The temperature was kept constant, up to 40°C.

GCMS analysis (uncorrected): 3S-caranepoxide (2) >99%.

Example 3.3 (process step a1b): Epoxidation of 3-carene to 3R-caranepoxide (more than 85% pure)

50 g of 3-carene (367 mmol, 1.0 eq.) was dissolved in 200 ml of acetone and 200 ml of water and cooled to 0°C. 72 g of N-bromosuccinimide (404 mmol, 1.1 equiv.) were added in portions, the internal temperature was maintained at 10°C, then stirred at room temperature for another 2 hours. Finally, 250 ml of 5M NaOH (5.5 ml/min) was added dropwise and stirred until complete conversion of the 3R-caranepoxide (0.5 h). The reaction mixture was combined with 200 ml of hexane and the phases were separated. The aqueous phase is extracted with 200 ml of hexane. The combined organic phases were washed with 250 ml of saturated sodium sulfite solution and 250 ml of water. Then separated the solvent under reduced pressure and 50°C. 50 g of 3R-caranepoxide (more than 85% pure) (312 mmol, 85%) were obtained.

Example 4.1 (process step e): oximation of 3S-caranone

A mixture enriched in 3S-caranone and 3R-caranone (80% purity, 85% 3S-caranone and 15% 3R-caranone) was dissolved in acetonitrile to c=2M. Then added 1.3 eq. NaOAc in the same volume of water and stirred for 5 min. Added 1.1 eq. HONH ₂ .HCl and stirred for an hour at 25°C.

GCMS analysis (uncorrected): total oxime 80%, of which 85% 3S-caranoxime and 15% 3R-caranoxime.

Mass spectrum:

MS (EI, 70 eV): m/z (%) = 168.05 (1.30), 167.00 (11.80), 166.05 (1.66), 153.10 (1.47), 152.05 (15.72), 151.05 (1.69), 150.05 (10.83), 149.05 (1.90), 148.10 (5.97), 139.10 (2.56).

MS (EI, 70 eV): % (m/z) = 100.00 (41.05), 51.40 (39.10), 47.59 (67.05), 43.19 (112.10), 42.42 (79.05), 41.89 (107.10), 40.65 (55.10), 39.11 (106.05), 38.33 (43.05), 29.88 (81.05).

Interpretation of the NMR spectrum:

¹ H NMR (400 MHz, DMSO-d6): δ/ppm=10.07 (s, 1H, -NO H ), 2.56 (dd, J=18.6, 1.6 Hz, 1H, -CNOH-C H ₂ -CH-) , 2.32-2.17 (m, 2H,-C H CH ₃ -, -CNOH-C H ₂ -CH-), 1.90-1.78 (m, J=16.8, 8.1, 3.1 Hz, 1H, -CHCH ₃ -C H ₂ -CH-), 1.37 (dt, J=14.4, 4.9 Hz, 1H, -CHCH ₃ -C H ₂ -CH-), 1.05 (d, J=7.1 Hz, 3H, CH ₂ -CHC H ₃ -CNOH -), 0.96 (s, 3H, -CCHCHC H ₃ CH ₃ -), 0.79 (td, J = 8.9, 1.8 Hz, 1H, -CNOH-CH ₂ -C H -) 0.71 (s, 3H, -CCHCHCH ₃ C H ₃ -), 0.69-0.62 (m, 1H, CHCH ₃ -CH ₂ -C H -).

¹³ C NMR (100 MHz, DMSO-d6): δ/ppm=161.5 (- C NOH-), 32.8 (- C HCH ₃ -), 28.5 (-CCHCH C H ₃ CH ₃ -), 26.8 (-CHCH ₃ - CH ₂ -CH-), 19.3 (CH ₂ -CH CH ₃ -CNOH-), 19.1 (-CNOH-CH ₂ -CH-), 18.3 ( C CHCHCH ₃ CH ₃ ), 17.1 (-CNOH- C H ₂ -CH-), 16.7 (-CHCH ₃ -CH ₂ -CH- ), 14.9 (-CCHCHCH ₃ C H ₃ -).

In FIG. 7 shows the 1H-NMR spectrum of 3S-caranoxime (in pure form), FIG. 8 shows the 13C-NMR spectrum of 3S-caranoxime (pure).

Example 4.2 (process step e): oximation of 3R-caranone

9.00 g of 3R-caranone (58 mmol) were dissolved in 60 ml of acetonitrile. Water was then added with 10.6 g of sodium acetate trihydrate (75 mmol) and 4.6 g of hydroxylamine hydrochloride (64 mmol) and stirred for 20 h at 60°C. The reaction mixture was washed with sodium bicarbonate solution and water, dried over magnesium sulfate and concentrated in vacuo. 5 g of the crude product was subjected to chromatographic purification (hexane/EtOAc). The yield was 3.6 g (72%) with a purity of 92%. The ratio of oximes was 85% 3R-caranoxime and 15% 3S-caranoxime.

Example 5.1.1 (process step f): Beckmann isomerization of 3S-caranoxime

The reaction mixture of example 4.1 (stage e) method) was cooled to 15°and slowly added 4 eq. NaOH in the form of 10M NaOH. After two hours of stirring at 15° C., 1 eq. p-toluenesulfonyl chloride and stirred for another two hours at room temperature. The aqueous phase was separated and extracted with ethyl acetate (double volume). The organic phases were washed with half-saturated sodium hydrogen carbonate solution (2.times.) and then with saturated sodium chloride solution.

GCMS analysis (uncorrected): Total purity of caranlactam 62%, 94.9% 3S-caranlactam and 5.1% 3R-caranlactam.

Mass spectrum:

MS (EI, 70 eV): m/z (%) = 168.10 (1.05), 167.15 (8.33), 166.25 (0.70), 154.20 (0.30), 153.20 (4.44), 152.20 (44.99), 151.25 (0.22), 150.20 (0.23), 139.20 (1.42), 138.15 (1.09).

MS (EI, 70 eV): % (m/z) = 100.00 (44.10), 60.39 (67.10), 44.99 (152.20), 44.18 (81.10), 42.43 (82.10), 37.54 (110.15), 35.25 (41.05), 28.11 (57.10), 19.97 (39.05), 19.46 (55.10).

In FIG. 9 shows the 1H-NMR spectrum of 3S-caranlactam (pure), FIG. 10 shows the 13C-NMR spectrum of 3S-caranlactam (pure).

Interpretation of the NMR spectrum:

¹ H NMR (400 MHz, DMSO-d6): δ/ppm=6.92 (s, 1H, -CO-N H -) 3.5-3.14 (m, 1H, -NH-C H CH ₃ -CH ₂ -), 2.31-2.15 (m, 2H, -CO-C H ₂ -CH-), 1.71-1.49 (m, 2H, -CH-C H ₂ -CCHCH ₃ -), 1.05 (d, J =6.4 Hz, 3H, -NH-CHC H ₃ -), 1.01 (s, 3H, -CC H CHCH ₃ C H ₃ -), 0.97 (s, 3H, -CCHCHC H ₃ CH ₃ -), 0.85-0.76 (m, 1H, - CC H CHCH ₃ CH ₃ -), 0.57 (td, J =9.0, 2.1 Hz, 1H, -CCHC H CH ₃ CH ₃ -).

¹³ C NMR (100 MHz, DMSO-d6): δ/ppm=173.8 (- C O-), 46.3 (-NH- C HCH ₃ -), 30.6 (-CO-C H ₂ -CH-), 30.4 ( CH-C H ₂ - CHCH3-), 28.6 (-CCHCH C H ₃ CH ₃ -), 21.11 (-NH-CH C H ₃ -), 20.1 (CO-CH ₂ - C H-), 20.1 (-CHCH ₃ -CH ₂ - C H-), 17.4 (- C CHCHCH ₃ CH ₃ -), 14.9 (-CCHCHCH ₃ C H ₃ -).

Example 5.1.2 (process step f2): Beckmann catalytic isomerization of 3S-caranoxime

167 mg of 3S-caranoxime (1.0 mmol) was dissolved in 2 ml of MeCN and heated under reflux. Then added 7.5 mol%. Zn(ClO ₄ ) ₂ ·6H ₂ O and stirred for 48 hours. The solvent was removed under reduced pressure, the residue was dissolved in ethyl acetate and washed several times with half-saturated sodium hydrogen carbonate solution and water. After crystallization from ethyl acetate, 120 mg of 3S-caranlactam (72%) were obtained.

Example 5.2 (process steps e) and f2): Oximation and Beckmann isomerization in one step (in one reactor)

35 mg of a mixture of 3S-caranone (15%) and 3R-caranone (85%) was dissolved in 280 ml of acetonitrile (MeCN) and mixed with 280 ml of water and 50 g of sodium acetate. Then 19.5 g of hydroxylamine hydrochloride was added and stirred for 48 hours at room temperature. The phases were separated, 270 ml of 3M NaOH were added in portions to the organic phases while cooling in an ice bath. The reaction mixture was stirred for 2 hours in an ice bath, then 53.2 g of tosyl chloride were added in portions. The reaction mixture was stirred for 4 hours, then washed with 2M hydrochloric acid, sodium hydrogen carbonate and half-saturated sodium chloride solution. The solvent was removed under reduced pressure, and the resulting crude product was crystallized several times from ethyl acetate. 7.90 g (20%) of pure 3R-caranlactam was obtained.

Example 6.1 (process steps g) and h): preparation of crystalline 3S-caranlactam

The reaction mixture of example 5 (stage f) method) was subjected to fractional distillation for almost complete crystallization of 3S-caranlactam. The rest of the 3R-caranlactam did not crystallize under the reaction conditions, so it was removed in the next distillation step (process step h) to give 3S-caranlactam. With said distillation, 3R-caranlactam can be obtained as a distillate.

Example 6.2 (process steps g) and h): preparation of 3R-caranlactam

3R-caranlactam could be obtained as a pure product from the mother liquor (remaining solution of example 6.1) of the synthesis of 3S-caranlactam after distillation (boiling point 350°C) and multiple recrystallization (ethyl acetate).

Example 6.3 (process steps g) and h): preparation of 3R-caranlactam

3.50 g of 3R-caranoxime (21 mmol) were dissolved in 25 ml of acetonitrile and cooled in an ice bath. Then 33 ml of 2M NaOH was added in portions and stirred for 2 hours. Then 4.50 g of tosyl chloride (23 mmol) were added in portions and stirred in an ice bath for 2.5 hours. The reaction mixture was washed with sodium bicarbonate solution and water, dried over magnesium sulfate and concentrated in vacuo. The crude product was recrystallized from ethyl acetate at -20° C. to give 2.61 g (75%) of 3R-caranlactam.

Example 7.1 (process step i): polymerization of 3S-caranlactam to 3S-polycaranamide

300 mg 3S-caranlactam (1.8 mmol), 10 mg N-benzoyl-3S-caranlactam (Bz-5, 0.036 mmol) and 0.5 mg NaH on paraffin (0.02 mmol) were mixed in a vacuum glass vessel and evacuated 10 min at 2 mbar. The reaction vessel was placed in a 180° C. oil bath and the contents were stirred. After about 20 seconds, polymerization was complete, the polymer was slowly cooled to room temperature, and partially crystalline 3S-polycaranamide was obtained. NMR analysis showed the presence of isotactic homopolymers.

Example 7.1.1 (process step i): polymerization of 3S-caranlactam to 3S-polycaranamide

300 mg 3S-caranlactam (1.8 mmol), 10 mg N-benzoyl-3S-caranlactam (Bz-5, 0.036 mmol) and 0.5 mg NaH on paraffin (0.02 mmol) were mixed in a vacuum glass vessel and evacuated 10 min at 2 mbar. The reaction vessel was placed in a 180° C. oil bath and the contents were stirred. The reaction mixture was held for five minutes at this temperature, then slowly cooled to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Received partially crystalline 3S-polycaranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC analysis (3.1)

Tg (mid point): 115°C

Tm (range): 260-290°C

Mn: 10.5 kDa (GPC method 4.2)

Mw: 16.8 kDa (GPC method 4.2)

PD: 1.6

1H: fig. eleven

13C: FIG. 12

COZY: fig. 13

HSQC: fig. 14

DEPT: fig. 15

DSC: fig. 25

GPC: fig. 51

Crystallinity: partly crystalline

Example 7.1.2 (process step i): polymerization of 3S-caranlactam to 3S-polycaranamide

300 mg of 3S-caranlactam (1.8 mmol), 5.4 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.02 mmol) and 3.5 mg of NaH on paraffin (0.09 mmol) were mixed under vacuum glass vessel and evacuated for 10 min at 2 mbar. The reaction vessel was placed in a 180° C. oil bath and the contents were stirred. The reaction mixture was kept for 1.5 h at this temperature, then cooled in air to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Received partially crystalline 3S-polycaranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC analysis (3.1)

Tg (mid point): 115°C

Tm (range): 250-285°C

Mn: 10.2 kDa (GPC method 4.2)

Mw: 16.2 kDa (GPC method 4.2)

PD: 1.6

DSC: fig. 26

GPC: fig. 52

Crystallinity: partly crystalline

Example 7.1.3 (process step i): polymerization of 3S-caranlactam to 3S-polycaranamide

302 mg of 3S-caranlactam (1.81 mmol), 9.8 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.036 mmol) and 0.9 mg of NaH on paraffin (0.02 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min at 2 mbar. The reaction vessel was placed in a 180° C. oil bath and the contents were stirred. The reaction mixture was kept for 1 h at this temperature, then slowly cooled to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Received partially crystalline 3S-polycaranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC analysis (3.1)

Tg (mid point): 115°C

Tm (range): 260-290°C

Mn: 9.3 kDa (GPC method 4.2)

Mw: 14.5 kDa (GPC method 4.2)

PD: 1.6

DSC: fig. 27

GPC: fig. 53

Crystallinity: partly crystalline

Example 7.1.4 (process step i): polymerization of 3S-caranlactam to 3S-polycaranamide

305 mg of 3S-caranlactam (1.84 mmol), 10.7 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.039 mmol) and 1.6 mg of NaH on paraffin (0.04 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min at 2 mbar. The reaction vessel was placed in a 180° C. oil bath and the contents were stirred. The reaction mixture was kept for 1 h at this temperature, then slowly cooled to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Received partially crystalline 3S-polycaranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC analysis (3.1)

Tg (midpoint): 113°C

Tm (range): 255-285°C

Mn: 9.1 kDa (GPC method 4.2)

Mw: 14.1 kDa (GPC method 4.2)

PD: 1.3

DSC: fig. 28

GPC: fig. 54

Crystallinity: partly crystalline

Example 7.1.5 (process step i): Polymerization of 3S-caranlactam to 3S-polycaranamide

308 mg of 3S-caranlactam (1.84 mmol), 20.7 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.076 mmol) and 4.0 mg of NaH on paraffin (0.1 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min at 2 mbar. The reaction vessel was placed in a 180° C. oil bath and the contents were stirred. The reaction mixture was kept for 1 h at this temperature, then slowly cooled to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Received partially crystalline 3S-polycaranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC analysis (3.1)

Tg (midpoint): 111°C

Tm (range): 245-285°C

Mn: 6.7 kDa (GPC method 4.2)

Mw: 9.5 kDa (GPC method 4.2)

PD: 1.4

DSC: fig. 29

GPC: fig. 55

Crystallinity: partly crystalline

Example 7.1.6 (process step i): polymerization of 3S-caranlactam to 3S-polycaranamide

300 mg of 3S-caranlactam (1.80 mmol), 30.0 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.11 mmol) and 3.9 mg of NaH on paraffin (0.10 mmol) were mixed under vacuum glass vessel and evacuated for 10 min at 2 mbar. The reaction vessel was placed in a 180° C. oil bath and the contents were stirred. The reaction mixture was kept for 1 h at this temperature, then slowly cooled to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Received partially crystalline 3S-polycaranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC analysis (3.1)

Tg (mid point): 105°C

Tm (range): 240-280°C

Mn: 5.9 kDa (GPC method 4.2)

Mw: 8.3 kDa (GPC method 4.2)

PD: 1.4

DSC: fig. thirty

GPC: fig. 56

Crystallinity: partly crystalline

Example 7.1.7 (process step i): polymerization of 3S-caranlactam to 3S-polycaranamide

300 mg of 3S-caranlactam (1.8 mmol), 4.9 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.02 mmol) and 4.0 mg of NaH on paraffin (0.1 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min at 2 mbar. The reaction vessel was placed in a 220° C. oil bath, and the contents were stirred. The reaction mixture was kept for 1 h at this temperature, then slowly cooled to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Received partially crystalline 3S-polycaranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC analysis (3.1)

Tg (mid point): 112°C

Tm (range): 240-275°C

Mn: 7.5 kDa (GPC method 4.2)

Mw: 9.6 kDa (GPC method 4.2)

PD: 1.3

DSC: fig. 31

GPC: fig. 57

Crystallinity: partly crystalline

Example 7.1.8 (process step i): polymerization of 3S-caranlactam to 3S-polycaranamide

300 mg of 3S-caranlactam (1.8 mmol), 10.6 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.04 mmol) and 3.8 mg of NaH on paraffin (0.1 mmol) were mixed under vacuum glass vessel and evacuated for 10 min at 2 mbar. The reaction vessel was placed in a 220° C. oil bath, and the contents were stirred. The reaction mixture was kept for 1 h at this temperature, then slowly cooled to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Received partially crystalline 3S-polycaranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC analysis (3.1)

Tg (mid point): 112°C

Tm (range): 230-270°C

Mn: 7.1 kDa (GPC method 4.2)

Mw: 9.0 kDa (GPC method 4.2)

PD: 1.3

DSC: fig. 32

GPC: fig. 58

Crystallinity: partly crystalline

Example 7.1.9 (process step i): polymerization of 3S-caranlactam to 3S-polycaranamide

309 mg of 3S-caranlactam (1.85 mmol), 19.6 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.07 mmol) and 4.0 mg of NaH on paraffin (0.1 mmol) were mixed under vacuum glass vessel and evacuated for 10 min at 2 mbar. The reaction vessel was placed in a 220° C. oil bath, and the contents were stirred. The reaction mixture was kept for 1 h at this temperature, then slowly cooled to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Received partially crystalline 3S-polycaranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC analysis (3.1)

Tg (mid point): 110°C

Tm (range): 240-280°C

Mn: 6.0 kDa (GPC method 4.2)

Mw: 7.5 kDa (GPC method 4.2)

PD: 1.3

DSC: fig. 33

GPC: fig. 59

Crystallinity: partly crystalline

Example 7.1.10 (process step i): Polymerization of 3S-caranlactam to 3S-polycaranamide

300 mg of 3S-caranlactam (1.83 mmol), 30.0 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.11 mmol) and 3.8 mg of NaH on paraffin (0.1 mmol) were mixed under vacuum glass vessel and evacuated for 10 min at 2 mbar. The reaction vessel was placed in a 220° C. oil bath, and the contents were stirred. The reaction mixture was kept for 1 h at this temperature, then slowly cooled to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Received partially crystalline 3S-polycaranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC analysis (3.1)

Tg (midpoint): 109°C

Tm (range): 230-270°C

Mn: 5.6 kDa (GPC method 4.2)

Mw: 7.3 kDa (GPC method 4.2)

PD: 1.3

DSC: fig. 34

GPC: fig. 60

Crystallinity: partly crystalline

Example 7.1.11 (process step i): polymerization of 3S-caranlactam to 3S-polycaranamide

523 mg of 3S-caranlactam (3.1 mmol), 10.4 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.038 mmol) and 3.7 mg of NaH on paraffin (0.09 mmol) were mixed in a glass reaction vessel under nitrogen atmosphere and polymerization was carried out for one hour in a heating block at 190°C. The polymerizate was dissolved directly in hexafluoroisopropanol (HFIP) and samples were taken for analysis by GPC and NMR.

Mn: 8.6 kDa (GPC method 4.2)

Mw: 16.9 kDa (GPC method 4.2)

PD: 2.0

GPC: fig. 61

Example 7.1.12 (process step i): polymerization of 3S-caranlactam to 3S-polycaranamide

500 mg of 3S-caranlactam (3.0 mmol) in a flask under an inert atmosphere at 190° C. was melted with stirring. Then 5.0 mg of NaH on paraffin (0.13 mmol) and 4.5 μl of acetic anhydride (0.048 mmol) were added. After solidification, the reaction mixture was slowly cooled to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Received amorphous poly-3S-caranamide. NMR analysis showed the presence of isotactic homopolymers.

Mn: 1.4 104 g/mol (GPC method 4.1)

Mw: 65.2 106 g/mol (GPC method 4.1)

Tg: 110-120°C (DSC method 3)

Tm: 260-290°C (DSC method 3)

GPC: fig. 78

DSC: fig. 81

Crystallinity: partly crystalline

Example 7.2 (process step i): polymerization of 3R-caranlactam to 3R-polycaranamide

300 mg of 3R-caranlactam (1.8 mmol), 10 mg of N-benzoyl-3R-caranlactam (0.036 mmol) and 0.5 mg of NaH on paraffin (0.02 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min at 2 mbar The reaction vessel was placed in a 170° C. oil bath and the contents were stirred. After about 20 seconds, the polymerization was completed, the polymer was slowly cooled to room temperature and amorphous 3R-polycaranamide was obtained. NMR analysis showed the presence of isotactic homopolymers.

Example 7.2.1 (process step i): polymerization of 3R-caranlactam to 3R-polycaranamide

500 mg of 3R-caranlactam (3.0 mmol) in a flask under an inert atmosphere at 170° C. was melted with stirring. Then 3.0 mg of NaH on paraffin (0.08 mmol) and 1.5 μl of acetic anhydride (0.016 mmol) were added. The reaction mixture was kept at this temperature for 20 seconds, then slowly cooled to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Received amorphous poly-3R-caranamide. NMR analysis showed the presence of isotactic homopolymers.

Tg (mid point): 122°C (DSC method 3.2)

Tm (range): none (DSC method 3.2)

Tg: 110-120°C (DSC method 3)

Tm (range): none (DSC method 3)

Mn: 1.1 10 ⁵ g/mol (GPC method 4.1)

Mw: 3.0 10 ⁵ g/mol (GPC method 4.1)

Mn: 33.3 kDa (GPC method 4.2)

Mw: 64.7 kDa (GPC method 4.2)

PD: 1.9

1H: fig. 16

13C: FIG. 17

COZY: fig. 18

HSQC: fig. 19

DEPT: fig. 20

DSC: fig. 82 (DSC method 3)

DSC: fig. 35 (DSC method 3.2)

GPC: fig. 62

GPC: fig. 79

Crystallinity: amorphous

Example 7.2.2 (process step i): polymerization of 3R-caranlactam to 3R-polycaranamide

500 mg of 3R-caranlactam (3.0 mmol) in a flask under an inert atmosphere at 170° C. was melted with stirring. Then 5.0 mg of NaH on paraffin (0.13 mmol) and 4.5 μl of acetic anhydride (0.05 mmol) were added. The reaction mixture was kept at this temperature for 30 min, then slowly cooled to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Received amorphous poly-3R-caranamide. NMR analysis showed the presence of isotactic homopolymers.

Mn: 29.5 kDa (GPC method 4.2)

Mw: 55.2 kDa (GPC method 4.2)

PD: 1.9

GPC: fig. 63

Example 7.2.3 (process step i): polymerization of 3R-caranlactam to 3R-polycaranamide

1.0 g of 3R-caranlactam (6.0 mmol), 14.6 mg of potassium (0.37 mmol) and 20 μl of benzoyl chloride (0.17 mmol) were polymerized in a flask under an inert atmosphere at 150° C. with stirring. The reaction mixture was kept at this temperature for 6 h, then slowly cooled to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Received amorphous poly-3R-caranamide. NMR analysis showed the presence of isotactic homopolymers.

Mn: 22.4 kDa (GPC method 4.2)

Mw: 38.1 kDa (GPC method 4.2)

PD: 1.7

GPC: fig. 64

GPC: fig. 79

Example 7.2.4 (process step i): polymerization of 3R-caranlactam to 3R-polycaranamide

511 mg of 3R-caranlactam (3.1 mmol), 0.6 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.002 mmol) and 3.5 mg of NaH on paraffin (0.09 mmol) were mixed in a glass reaction vessel under nitrogen atmosphere and polymerization was carried out for one hour at 190°C. The polymerizate was dissolved directly in hexafluoroisopropanol (HFIP) and samples were taken for analysis by GPC and NMR. Received amorphous poly-3R-caranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC 3.2 analysis

Tg (mid point): 119 °C

Tm (range): none

Mn: 19.9 kDa (GPC method 4.2)

Mw: 32.9 kDa (GPC method 4.2)

PD: 1.7

DSC: fig. 36

GPC: fig. 65

Crystallinity: amorphous

Example 7.2.5 (process step i): polymerization of 3R-caranlactam to 3R-polycaranamide

506 mg of 3R-caranlactam (3.0 mmol), 1.03 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.004 mmol) and 3.3 mg of NaH on paraffin (0.08 mmol) were mixed in a glass reaction vessel under nitrogen atmosphere and polymerization was carried out for one hour in a heating block at 190°C. The polymerizate was dissolved directly in hexafluoroisopropanol (HFIP) and samples were taken for analysis by GPC and NMR. Received amorphous poly-3R-caranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC 3.2 analysis

Tg (mid point): 120 °C

Tm (range): none

Mn: 20.2 kDa (GPC method 4.2)

Mw: 43.8 kDa (GPC method 4.2)

PD: 2.2

DSC: fig. 37

GPC: fig. 66

Crystallinity: amorphous

Example 7.2.6 (process step i): polymerization of 3R-caranlactam to 3R-polycaranamide

505 mg 3R-caranlactam (3.0 mmol), 2.45 mg N-benzoyl-3S-caranlactam (Bz-5, 0.009 mmol) and 3.3 mg NaH on paraffin (0.08 mmol) were polymerized in a glass reaction vessel in a nitrogen atmosphere in a heating block for one hour at 190°C. The polymerizate was dissolved directly in hexafluoroisopropanol (HFIP) and samples were taken for analysis by GPC and NMR. Received amorphous poly-3R-caranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC 3.2 analysis

Tg (mid point): 117 °C

Tm (range): none

Mn: 19.6 kDa (GPC method 4.2)

Mw: 45.6 kDa (GPC method 4.2)

PD: 2.3

DSC: fig. 38

GPC: fig. 67

Crystallinity: amorphous

Example 7.2.7 (process step i): polymerization of 3R-caranlactam to 3R-polycaranamide

508 mg of 3R-caranlactam (3.0 mmol), 5.13 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.02 mmol) and 3.2 mg of NaH on paraffin (0.08 mmol) were polymerized in a glass reaction vessel under nitrogen atmosphere in a heating block for one hour at 190°C. The polymerizate was dissolved directly in hexafluoroisopropanol (HFIP) and samples were taken for analysis by GPC and NMR. Received amorphous poly-3R-caranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC 3.2 analysis

Tg (mid point): 116 °C

Tm (range): none

Mn: 15.2 kDa (GPC method 4.2)

Mw: 36.3 kDa (GPC method 4.2)

PD: 2.4

DSC: fig. 39

GPC: fig. 68

Crystallinity: amorphous

Example 7.2.8 (process step i): Polymerization of 3R-caranlactam to 3R-polycaranamide

513 mg of 3R-caranlactam (3.1 mmol), 7.50 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.03 mmol) and 3.5 mg of NaH on paraffin (0.09 mmol) were polymerized in a glass reaction vessel under nitrogen atmosphere in a heating block for one hour at 190°C. The polymerizate was dissolved directly in hexafluoroisopropanol (HFIP) and samples were taken for analysis by GPC and NMR. Received amorphous poly-3R-caranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC 3.2 analysis

Tg (mid point): 115 °C

Tm (range): none

Mn: 13.5 kDa (GPC method 4.2)

Mw: 31.8 kDa (GPC method 4.2)

PD: 2.3

DSC: fig. 40

GPC: fig. 69

Crystallinity: amorphous

Example 7.2.9 (process step i): polymerization of 3R-caranlactam to 3R-polycaranamide

512 mg of 3R-caranlactam (3.1 mmol), 10.2 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.04 mmol) and 3.4 mg of NaH on paraffin (0.09 mmol) were polymerized in a glass reaction vessel under nitrogen atmosphere in a heating block for one hour at 190°C. The polymerizate was dissolved directly in hexafluoroisopropanol (HFIP) and samples were taken for analysis by GPC and NMR. Received amorphous poly-3R-caranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC 3.2 analysis

Tg (mid point): 117 °C

Tm (range): none

Mn: 13.1 kDa (GPC method 4.2)

Mw: 29.7 kDa (GPC method 4.2)

PD: 2.3

DSC: fig. 41

GPC: fig. 70

Crystallinity: amorphous

Example 7.2.10 (process step i): polymerization of 3R-caranlactam to 3R-polycaranamide

900 mg of 3R-caranlactam (5.39 mmol), 5.5 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.009 mmol) and 7.5 mg of NaH on paraffin (0.19 mmol) were mixed in a vacuum glass vessel and 10 min was evacuated at 2 mbar. The reaction vessel was placed in a 170° C. oil bath and the contents were stirred. The reaction mixture was kept for 30 min at this temperature, then slowly cooled to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Received amorphous poly-3R-caranamide. NMR analysis showed the presence of isotactic homopolymers.

DSC 3.2 analysis

Tg (mid point): 112 °C

Tm (range): none

Mn: 24.6 kDa (GPC method 4.2)

Mw: 55.5 kDa (GPC method 4.2)

PD: 2.3

DSC: fig. 42

GPC: fig. 71

Crystallinity: amorphous

Example 7.3 (process step i): polymerization of 3S-caranlactam with 3R-caranlactam to 3S/3R-co-polycaranamide

150 mg 3R-caranlactam (0.9 mmol), 150 mg 3S-caranlactam (0.9 mmol), 10 mg N-benzoyl-3S-caranlactam (0.036 mmol) and 0.5 mg NaH on paraffin (0.02 mmol ) was mixed in a vacuum glass vessel and evacuated at 2 mbar for 10 min. The reaction vessel was placed in a 180° C. oil bath and the contents were stirred. After about 20 sec, the polymerization was completed, the polymer was slowly cooled to room temperature, and an amorphous 3S/3R-polycaranamide was obtained.

Example 7.3.1 (process step i): Polymerization of 3S-caranlactam and 3R-caranlactam to 3S-caranlactam-3R-caranlactam-polycaranamide

250 mg of 3R-caranlactam (1.5 mmol) and 250 mg of 3S-caranlactam (1.5 mmol) in an inert atmosphere at 190° C. were melted in a flask with stirring. Then 5.0 mg of NaH on paraffin (0.13 mmol) and 4.5 μl of acetic anhydride (0.048 mmol) were added. The reaction mixture was kept for 30 min at this temperature, then slowly cooled to room temperature. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Amorphous 3S-caranlactam-3R-caranlactam-polycaranamide was obtained.

Tg (mid point): 112°C (DSC method 3.2)

Tm (range): none (DSC method 3.2)

Tg: 110-120°C (DSC method 3)

Tm (range): none (DSC method 3)

Mn: 3.2 10 ⁴ (GPC method 4.1)

Mw: 1.1 10⁵ (GPC method 4.1)

1H: fig. 21

13C: FIG. 22

DSC: fig. 43

DSC: fig. 83

GPC: fig. 80

Crystallinity: amorphous

Example 7.3.2 (process step i): Polymerization of 3S-caranlactam and 3R-caranlactam to 3S-caranlactam-3R-caranlactam-polycaranamide

750 mg 3S-caranlactam (5.5 mmol), 362 mg caprolactam (0.9 mmol) 20.2 mg N-benzoyl-3S-caranlactam (Bz-5, 0.07 mmol) and 8.0 mg NaH on paraffin (0.20 mmol) was polymerized in a glass reaction vessel under nitrogen in a heating block for one hour at 190°C. The resulting polymer was crushed. The remaining monomers and soluble oligomers were removed by boiling under reflux in a mixture of water and ethanol (1:1). Partially crystalline 3S-caranlactam-3R-caranlactam-co-polyamide was obtained.

DSC 3.2 analysis

Mn: 10.4 kDa (GPC method 4.2)

Mw: 15.0 kDa (GPC method 4.2)

PD: 1.4

Tg (mid point): 109°C

Tm (range): 210-250°C

DSC: fig. 44

GPC: fig. 72

Crystallinity: partly crystalline

Example 8 (process step i2): copolymerization of 3S-caranlactam with laurinlactam

5.00 g of laurinlactam (26 mmol) were melted at 190° C. and 2.50 g of 3S-caranlactam (15 mmol) were dissolved therein. Then 75 g of N-benzoyl-3S-caranlactam (IUPAC: (1R,5S,7S)-4-benzoyl-5,8,8-trimethyl-4-azabicyclo[5.1.0]octan-3-one) and 50 mg 60% NaH on paraffin wax. After completion of polymerization, the temperature was maintained at 190°C for 30 min, then, without active cooling, it was allowed to cool to room temperature. The resulting polymer was crushed and stirred in a mixture of ethanol-water (1:1) for 24 h at the reflux temperature. After filtration, the resulting polymer was dried for 16 h at 120°C.

Glass transition temperature Tg (range): 40-50°C

Melting point Tm (range): not determined

Crystallinity: amorphous

Example 8.1.1 (process step i2): polymerization of 3S-caranlactam and laurinlactam to 3S-caranlactam-laurinlactam-co-polycaranamide

1.0 g laurin lactam (5.0 mmol), 500 mg 3S-caranlactam (3.0 mmol), 50 mg N-benzoyl-3S-caranlactam (Bz-5, 0.18 mmol) and 18 mg NaH on paraffin were polymerized 1 h in a glass reaction vessel under nitrogen in an oil bath at 190°C. The remaining monomers and oligomers were separated by precipitation of the polymer from HFIP with ethanol. Amorphous 3S-caranlactam-laurinlactam-co-polycaranamide was obtained.

DSC 3.2 analysis

Tg (midpoint): 46°C

Tm (range): none

1H: fig. 23

Mn: 12.5 kDa (GPC method 4.2)

Mw: 24.5 kDa (GPC method 4.2)

PD: 2.0

DSC: fig. 45

GPC: fig. 73

Crystallinity: amorphous

Example 8.1.2 (process step i2): polymerization of 3S-caranlactam and laurinlactam to 3S-caranlactam-laurinlactam-co-polycaranamide

10 g laurinlactam (50 mmol), 5 g 3S-caranlactam (30 mmol), 54 mg N-benzoyl-3S-caranlactam (Bz-5, 0.2 mmol) and 20 mg NaH on paraffin (0.50 mmol) were polymerized 1 h in a glass reaction vessel under nitrogen in an oil bath at 190°C. The remaining monomers and oligomers were separated by precipitation of the polymer from HFIP with ethanol. Amorphous 3S-caranlactam-laurinlactam-co-polycaranamide was obtained.

DSC 3.2 analysis

1H: fig. 23

Mn: 30.2 kDa (GPC method 4.2)

Mw: 60.1 kDa (GPC method 4.2)

PD: 2.0

Tg (mid point): 49°C

Tm (range): none

DSC: fig. 46

GPC: fig. 74

Crystallinity: amorphous

Example 8.1.3 (process step i2): polymerization of 3S-caranlactam and laurinlactam to 3S-caranlactam-laurinlactam-co-polycaranamide

411 mg 3S-caranlactam (2.5 mmol), 486 mg laurinlactam (2.5 mmol), 20.0 mg N-benzoyl-3S-caranlactam (Bz-5, 0.07 mmol) and 8.0 mg NaH per paraffin (0.20 mmol) was polymerized for 1 h in a glass reaction vessel under nitrogen in a heating block at 190°C. The remaining monomers and oligomers were separated by precipitation of the polymer from HFIP with ethanol. Amorphous 3S-caranlactam-laurinlactam-co-polycaranamide was obtained.

DSC 3.2 analysis

Mn: 10.0 kDa (GPC method 4.2)

Mw: 15.6 kDa (GPC method 4.2)

PD: 1.6

Tg (mid point): 55°C

Tm (range): none

DSC: fig. 47

GPC: fig. 75

Crystallinity: amorphous

Example 8.2.1 (process step i2): polymerization of 3S-caranlactam and caprolactam to 3S-caranlactam-caprolactam-co-polycaranamide

5.0 g caprolactam (44 mmol), 2.5 g 3S-caranlactam (15 mmol), 75 mg N-benzoyl-3S-caranlactam (Bz-5, 0.28 mmol) and 50 mg NaH on paraffin (1, 3 mmol) was polymerized for 1 h in a glass reaction vessel under nitrogen in an oil bath at 190°C. The remaining monomers and oligomers were separated by precipitation of the polymer from HFIP with ethanol. Partially crystalline 3S-caranlactam-caprolactam-co-polycaranamide was obtained.

DSC 3.2 analysis

Mn: 15.2 kDa (GPC method 4.2)

Mw: 31.1 kDa (GPC method 4.2)

PD: 2.0

Tg (midpoint): 62°C

Tm (range): 160-190°C

DSC: fig. 48

GPC: fig. 76

Crystallinity: partly crystalline

Example 8.2.2 (process step i2): polymerization of 3S-caranlactam and caprolactam to 3S-caranlactam-caprolactam-co-polycaranamide

537 mg 3S-caranlactam (3.2 mmol), 362 mg caprolactam (3.2 mmol), 20.1 mg N-benzoyl-3S-caranlactam (Bz-5, 0.07 mmol) and 7.9 mg NaH per paraffin (0.20 mmol) was polymerized for 1 h in a glass reaction vessel under nitrogen in a heating block at 190°C. The resulting polymer was crushed. The remaining monomers and oligomers were separated by boiling under reflux in a mixture of water and ethanol (1:1). Amorphous 3S-caranlactam-caprolactam-co-polycaranamide was obtained.

DSC 3.2 analysis

Mn: 12.1 kDa (GPC method 4.2)

Mw: 17.3 kDa (GPC method 4.2)

PD: 1.4

Tg (mid point): 88°C

Tm (range): none

DSC: fig. 49

GPC: fig. 77

Crystallinity: amorphous

Example 8.2.3 (process step i2): polymerization of 3S-caranlactam and caprolactam to 3S-caranlactam-caprolactam-co-polycaranamide

250 mg 3S-caranlactam (1.5 mmol), 57 mg caprolactam (0.5 mmol), 10 mg N-benzoyl-3S-caranlactam (Bz-5, 0.04 mmol) and 1.5 mg NaH on paraffin ( 0.04 mmol) was polymerized for 1 hour in a glass reaction vessel under nitrogen in a heating block at 175°C. The resulting polymer was crushed. The remaining monomers and oligomers were separated by precipitation of the polymer from HFIP with ethanol. Amorphous 3S-caranlactam-caprolactam-co-polycaranamide was obtained.

DSC 3.2 analysis

Tg (mid point): 99°C

Tm (range): none

DSC: fig. 50

Crystallinity: amorphous

Example 9 (process step i2): copolymerization of 3S-caranlactam with caprolactam

5.00 g of caprolactam (44 mmol) were melted at 190° C. and 2.50 g of 3S-caranlactam (15 mmol) were dissolved therein. Then 75 g of N-benzoyl-3S-caranlactam (IUPAC: (1R,5S,7S)-4-benzoyl-5,8,8-trimethyl-4-azabicyclo[5.1.0]octan-3-one) and 50 mg 60% NaH on paraffin wax. After completion of polymerization, the temperature was maintained at 190°C for 30 min, then, without active cooling, it was allowed to cool to room temperature. The resulting polymer was crushed and stirred in a mixture of ethanol-water (1:1) for 24 h at the reflux temperature. After filtration, the resulting polymer was dried for 16 h at 120°C.

Glass transition temperature Tg (range): 50-60°C

Melting point Tm (range): 160-200°C

Crystallinity: partly crystalline

Example 10 Water Absorption of 3R Polyamide

PA6 was prepared by ring-opening anionic polymerization (2.8 mmol caprolactam, 0.1 mmol 60% NaH on paraffin wax, 0.05 mmol Ac ₂ O, 180° C.). The remainder of the monomer was removed by boiling under reflux in a mixture of water/ethanol. 30-42 mg of PA6 (three samples) and two samples of poly-3R-caranamide were kept in a DSC (the same apparatus as described in relation to the DSC method (3)) at 230° C. for three minutes and thus uniform polyamide blocks were obtained. Weight was determined using an OHAUS Discovery DV215CD balance with a maximum error of 0.01 mg. The samples were then, in each case, stirred for three days in water at 25°C. The samples were then air dried and weighed after 30 minutes and four and a half hours. Finally, the samples were dried for three hours at 80°C and weighed. This time was sufficient for complete drying of the samples of poly-3R-caranamide. In general, the greater water absorption of PA6 and the longer drying time of PA6 indicates, in general, the lower water absorption of the aliphatic substituted poly-3R-caranamide compared to PA6.

Table 13: Water absorption, pre-treatment: A=polyamide block from DSC; B=water bath (3 days) and air dry (30 min); C=air drying (4.5 hours); D=drying at 80°C (3.0 h)

Preliminary processing A B C D Try Polyamide Sample weight, mg
Water absorption, % wt. 1 PA6-1 35.66 37.45
5.4 37.01
4.0 36.05
1.5 2 PA6-2 37.78 39.57
4.9 39.36
4.3 38.16
1.1 3 PA6-3 31.86 33.67
5.7 32.58
2.3 32.2
1.1 4 Poly-3R-caranamide-1 40.75 41.44
2.0 40.80
0.44 40.62
0 5 Poly-3R-caranamide-2 30.89 31.32
2.3 30.92
0.75 30.7
< 0.1

Example 11.1: Qualitative determination of the transparency of 3R polyamide compared to PA6 and PA12

The 3R-polyamide was dissolved in HFIP (25 mg/ml) and applied to the PTFE film by careful dropping. After evaporation of the solvent and drying for 3 hours at 85°C, a more transparent film with defects due to uneven evaporation and inclusion of air was obtained compared to PA6 and PA12.

Example 11.2: Qualitative determination of transparency of amorphous 3S-caranlactam-laurinlactam-co-polycaranamide compared to PA6 and PA12

Amorphous 3S-caranlactam-laurinlactam-co-polycaranamide was dissolved in HFIP (25 mg/ml) and transferred to a crystallizer (diameter 9 cm). After evaporation of the solvent and drying for 3 hours at 85°C, a more transparent film with defects due to uneven evaporation and inclusion of air was obtained compared to PA6 and PA12.

Example 11.3: Qualitative determination of transparency of amorphous 3S-caranlactam-caprolactam-co-polycaranamide compared to PA6 and PA12

Amorphous 3S-caranlactam-caprolactam-co-polycaranamide was dissolved in HFIP (25 mg/ml) and applied to a PTFE film by careful dropping. After evaporation of the solvent and drying for 3 hours at 85°C, a more transparent film with defects due to uneven evaporation and inclusion of air was obtained compared to PA6 and PA12.

Claims (51)

1. Polycaranamide, which is a 3S-polycaranamide of the following formula with n ≥ 2 repeat units: , or 3R-polycaranamide of the following formula with n ≥ 2 repeating units: . 2. 3S/3R-co-polycaranamide of the following formula with repeat units a, b and n, where n ≥ 2, and each of a and b is a natural number greater than or equal to 1 3. Co-polyamide derived from 3S-caranlactam, 3R-caranlactam or a mixture of 3S-caranlactam and 3R-caranlactam and at least one additional lactam. 4. Co-polyamide according to claim 3, wherein at least one additional lactam is caprolactam and/or laurin lactam. 5. Co-polyamide according to claim 3 or 4, containing at least one of the following repeating units corresponding to one of the following formulas, with the number of repeating units a, b, c and n, with n ≥ 2, each of a, b and c is a natural number greater than or equal to 1 , where A is the repeating unit of the additional lactam built into the co-polyamide. 6. A method for the production of an isomer-enriched mixture of 3S-caranone and 3R-caranone from 3-caranepoxide, comprising the following steps, in which: a) preparing a reaction mixture containing 3-caranepoxide and at least one acid catalyst, b) carry out the isomerization reaction of 3-caranepoxide in the reaction mixture at a temperature of from 20°C to 140°C, where the acid catalyst in the reaction mixture in stages a) and b) of the method is used at a concentration of from 0.01 to 2.0 mol%. relative to the 3-caranepoxide used, and c) an isomer-enriched mixture is obtained with an isomer ratio of at least 80% 3S-caranone or 3R-caranone relative to the total amount of caranone. 7. The method according to claim 6, wherein the reaction mixture prepared in step a) of the method further comprises a first organic solvent. 8. The method according to claim 6, wherein the 3-caranepoxide used in step a) of the process is 3S-caranepoxide and the isomer-enriched mixture obtained in step c) of the process is a mixture enriched in 3S-caranone with an isomer ratio of at least 80 % 3S-caranone relative to the total amount of caranone, therefore, 3R- and 3S-caranone. 9. The method according to claim 6, wherein the 3-caranepoxide used in step a) of the process is 3R-caranepoxide and the isomer-enriched mixture obtained in step c) of the process is a mixture enriched in 3R-caranone with an isomer ratio of at least 80 % 3R-caranone relative to the total amount of caranone. 10. Process according to claim 6, wherein the 3-caranepoxide used in process step a) is obtained in process step a1) by epoxidation of 3-carene. 11. A method for preparing a mixture of 3S-caranone and 3R-caranone enriched with 3R-caranone from 3-caranepoxide, comprising the following steps, in which: a) a reaction mixture is prepared containing 3-caranepoxide and at least one acid catalyst, the reaction mixture prepared in step a) of the process additionally containing a first organic solvent; b) carry out the isomerization reaction of 3-caranepoxide in the reaction mixture at a temperature of from 20°C to 140°C, where the acid catalyst in the reaction mixture in stages a) and b) of the method is used at a concentration of from 0.01 to 2.0 mol%. relative to the 3-caranepoxide used, and c) an isomer-enriched mixture is obtained with an isomer ratio of at least 80% 3S-caranone relative to the total caranone; d) isomerizing the 3S-caranone-enriched mixture obtained in step c) of the process in at least a second solvent in the presence of a base or Bronsted acid with a pKs of at most 0.7 to obtain a 3R-caranone-enriched mixture with an isomer content of at least 50% 3R-caranone relative to the total caranone, where the second organic solvent is an aprotic polar solvent with a relative polarity of at least 0.200 or a protic polar solvent with a relative polarity of at least 0.200. 12. A method for producing an isomer-enriched mixture of 3S-caranoxime and 3R-caranoxime from 3-caranepoxide, comprising the following steps, in which: i) an isomer-enriched mixture of 3S-caranone and 3R-caranone is obtained from 3-caranepoxide by the method according to any one of paragraphs. 6 or 11; ii) the isomer-enriched mixture of 3S- and 3R-caranone obtained in step c) or d) of the process is converted in an additional step e) in the presence of at least a third organic solvent, a base and hydroxylamine (HONH ₂ .HCl) into an enriched 3- caranoxime mixture with an isomer ratio of at least 80% 3S- or 3R-caranoxime relative to the total amount of caranoxime, that is, 3R- and 3S-caranoxime. 13. A method for producing an isomer-enriched mixture of 3S-caranlactam and 3R-caranlactam from 3-caranepoxide, comprising the following steps, in which: i) obtaining an isomer-enriched mixture of 3S-caranoxime and 3R-caranoxime from 3-caranepoxide by the method of claim 12; ii) the mixture enriched with 3-caranoxime obtained in step e) of the process is isomerized in an additional step f) to obtain a mixture enriched with 3-caranlactam in an isomer ratio of at least 80% of 3S- or 3R-caranlactam relative to the total amount of caranlactam, i.e., 3R- and 3S-caranlactam. 14. A method for producing 3S-caranlactam from 3-caranepoxide, comprising the following steps, in which: i) obtaining an isomer-enriched mixture of 3S-caranlactam and 3R-caranlactam from 3-caranepoxide by the method of claim 13; ii) from the 3-caranlactam enriched mixture obtained in step f), 3S-caranlactam is obtained by crystallization in step g) of the process. 15. A method for producing 3R-caranlactam from 3-caranepoxide, comprising the following steps, in which: i) obtaining an isomer-enriched mixture of 3S-caranlactam and 3R-caranlactam from 3-caranepoxide by the method of claim 13 or 14; ii) from the 3-caranlactam enriched mixture obtained in step f), 3R-caranlactam is obtained by separating the 3S-caranlactam in step h) of the process. 16. A method for producing isomer-enriched polycaranamide from 3-caranepoxide, comprising the following steps, in which: i) receive 3S-caranlactam, 3R-caranlactam or a mixture of 3S-caranlactam and 3R-caranlactam from 3-caranepoxide by the method according to any one of paragraphs. 13-15; ii) the 3S-caranlactam, 3R-caranlactam or mixture of 3R- and 3S-caranlactam obtained in step i) is polymerized into 3S-polycaranamide, 3R-polycaranamide or 3S/3R-co-polycaranamide. 17. A method for the production of 3S-caranlactam from 3-carene, where the method includes steps a) - c), e), f) and g) according to claim 14, where step a) of the method uses 3S- caranepoxide, in process step c) a mixture enriched in 3S-caranone is obtained with an isomer ratio of at least 80% of 3S-caranone relative to the total amount of caranone, in process step e) it is converted into a mixture enriched in 3S-caranoxime with an isomer ratio of at least , 80% of 3S-caranoxime relative to the total amount of caranoxime, in step f) of the process is converted into a mixture enriched in 3S-caranlactam with an isomer ratio of at least 80% of 3S-caranoxime relative to the total amount of caranoxime, and in step g) 3S is obtained by crystallization -caranlactam. 18. A method for the production of 3R-caranlactam from 3-carene, where the method includes steps a) - h) according to claim 15, where 3S-caranepoxide obtained by epoxidation of 3-carene is used at step a) of the method, at step c) of the method enriched 3S-caranone mixture with an isomer ratio of at least 80% 3S-caranone relative to the total amount of caranone, it is isomerized in step d) of the process into a mixture enriched in 3R-caranone with an isomer content of at least 50% 3R-caranone relative to the total amounts of caranone, in process step e) is converted into a mixture enriched in 3R-caranoxime with an isomer ratio of at least 50% of 3R-caranoxime relative to the total amount of caranoxime, in process step f) it is converted into a mixture enriched in 3R-caranoxime with an isomer ratio of at least 50% 3R-caranlactam relative to the total amount of caranlactam and after separating the 3S-caranlactam in step h) of the process, 3R-canarlactam is obtained. 19. 3S-caranoxime corresponding to the formula 20. 3S-caranoxime according to claim 19, obtained or obtained by the method according to claim 12. 21. 3S-karanlactam, corresponding to the formula: 22. 3S-caranlactam according to claim 21, obtained or obtained by the method according to claim 13 or 14. 23. Plastic product containing at least one of the polyamides according to any one of paragraphs. 1, 2, 3. 24. The plastic product of claim 23 wherein the polyamide is 3S-polycaranamide, 3R-polycaranamide, or co-polyamide. 25. A plastic product according to claim 23 or 24, where this product contains at least 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 95 or 99% by weight. polyamide. 26. A plastic product according to claim 23 or 24, wherein the product consists of at least one of said polyamides.

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