Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
  • C08G69/14—Lactams
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
  • C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C225/04—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated
  • C07C225/08—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and containing rings
  • C07C225/10—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and containing rings with doubly-bound oxygen atoms bound to carbon atoms not being part of rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C251/32—Oximes
  • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
  • C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
  • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
  • C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/385—Saturated compounds containing a keto group being part of a ring
  • C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
  • C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
  • C07C49/427—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having two rings
  • C07C49/433—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having two rings the condensed ring system containing seven carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
  • C07D201/02—Preparation of lactams
  • C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
  • C07D223/14—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D223/32—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom condensed with carbocyclic rings or ring systems containing carbocyclic rings other than six-membered
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
  • C07B2200/07—Optical isomers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2602/00—Systems containing two condensed rings
  • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
  • C07C2602/14—All rings being cycloaliphatic
  • C07C2602/20—All rings being cycloaliphatic the ring system containing seven carbon atoms

Definitions

• the present invention relates to a process for preparing an isomer-enriched mixture of 3S- and 3R-caranone (IUPAC: (IR, 4S, 6S) -4,7,7-trimethyl-bicyclo [4.l.0] -heptan-3-one and (IR, 4R, 6S) -4,7,7-trimethyl-bicyclo [4.1.0] heptan-3-one) from 3S-caranepoxide (IUPAC: (IS, 3S, 5R, 7R) -3.8, 8-trimethyl-4-oxatricyclo [5.1.10.03.5] octane), a 3S-caranone derived therefrom, a process for the preparation of 3S-caranlactam (IUPAC: (IR, 5S, 7S) -5,8,8 trimethyl-4-azabicyclo [5.1.0] octan-3-one) from (+) - 3-carene ((IS, 6R) -3,7,7-trimethyl-bic
• Polyamides are formed by linking bi-functional monomers with amino groups and, preferably activated, carboxyl groups. Both diamines with dicarboxylic acids and amino acids with amino acids can be reacted. In the latter, with the amino group and the carboxyl group, both functional groups required for linking are present in the same molecule.
• lactams such as e-caprolactam, e.g. be used by Ringöffhungspolymerisation for the production of polyamides.
• E-Caprolactam is industrially produced from cyclohexanone and laurolactam from cyclododecanone , This is the ketone first to the oxime and this oxime then again by a Beckmann rearrangement to lactam, so the monomer for the polyamide preparation implemented.
• Bio-based polyamides available in industrial quantities have hitherto been produced predominantly on the basis of castor oil.
• the monomers produced from fatty acids lead to
• linear, semi-crystalline polymer chains (PA11, PA410, PA610, PA1010, PA10.12) with comparable properties to fossil-based polyamides.
• the glass transition point (Tg) of the commercial fatty acid-based polyamides is generally below 60 ° C.
• the ⁇ -pinene-based polyamide described by Winnacker (M. Winnacker, J. Sag, A. Tischner, B. Rieger, Macromol, Rapid Commun., 2017, 38, 167878) has a Tg of 160 ° C. and a melting point ( Tm) of 264 ° C, but only molecular weights of about 24 kDa are achieved. Menthonlactam can only be converted to oligomers.
• Previously known terpene and fatty acid-based polyamides are partially crystalline.
• terpene- and fatty acid-based polyamides have hitherto been presented either predominantly with low molar masses or with a low glass transition point and thus a limited field of application.
• the syntheses of the respective monomers are usually not feasible on an industrial scale (terpene-based).
• renewable raw material which is used for the production of the monomer
• the renewable raw material obtained in the production of other products from renewable raw materials as residue / waste.
• residue / waste For example, in the production of pulp large amounts of terpenes, in particular a residue in the cellulose production from wood.
• Another disadvantage of previously known methods for the production of polyamides from renewable raw materials is that the monomers or intermediates used for the preparation of the polyamides on the synthesis route for these monomers often can not be obtained chemically pure and / or not isomerically pure.
• Another disadvantage is that the service temperatures of the polyamides are often not suitable for a variety of applications and also the achievable molar masses are low.
• the optical purity, that is (hereinafter abbreviated abbreviated) and the tacticity, as well as the crystallinity of the polyamides are not specifically adjustable.
• cleaning methods for example chromatographic separations, are available in chemistry in order to separate isomers, in particular isomeric intermediates for the preparation of the monomers or the isomeric monomers themselves, but these methods are often very complicated and expensive.
• the corresponding polyamides can thus be very expensive compared to polyamides from fossil raw materials.
• polyamides which are improved over known polyamides from non-renewable or petroleum-based raw materials, in particular by the methods provided polyamides, preferably improved transparency and / or strength and / or toughness and / or stereoregularity, especially for stereo- or enantioselective Applications.
• the object of the present invention is achieved in particular by the teaching of claim 1 and the further independent claims.
• the present invention solves the present technical problem in particular by providing polycaranamide, wherein the polycaranamide 3S-polycaranamide according to the formula (with n repeating units):
• the invention also relates to 3S-3R-copolycaranamides according to the formula (with a, b and n repeating units):
• the mentioned polycaranamides can be prepared in a preferred embodiment by the processes according to the present invention, in particular using processes according to the invention, the polycaranamides according to the invention of 3-carene, preferably 3-caranepoxide and in particular derived isomer-enriched mixtures of 3S-caranone and 3R-caranone, win.
• An essential contribution of the present invention is to provide from 3-carene or 3-caranepoxide via the process according to the invention the precursors for copolycaranamide synthesis, in particular 3S-caranone for the provision of 3S-polycaranamide.
• An advantageous embodiment of the invention provides for the preparation of 3S-caranone-enriched mixtures, in particular a 3S-caranone-enriched mixture, from which advantageously 3S-caranoxime and 3S-caranlactam as a precursor for the 3S-polycaranamide or a 3S-copolycaranamide let win.
• the present invention also relates to a process for preparing an isomer-enriched mixture of 3S-caranone and 3R-caranone from 3-caranepoxide, comprising the following process steps: a) providing a reaction mixture comprising 3-caranepoxide and at least one acidic catalyst, b) reaction of the 3-caranepoxide in the reaction mixture at a temperature of -40 ° C. to 140 ° C. with rearrangement and c) obtaining the isomer-enriched mixture having an isomer ratio of at least 80% 3S-caranone or 3R-caranone (based on total amount of caranone) ,
• the reaction mixture provided in process step a) additionally contains a first organic solvent.
• the present invention relates in particular to a process for preparing an isomer-enriched mixture of 3S-caranone and 3R-caranone from 3-caranepoxide, comprising the following process steps: a) providing a reaction mixture containing 3-caranepoxide, at least one acidic catalyst and at least one first organic solvent, b) reaction of the 3-caranepoxide in the reaction mixture at a temperature of -40 ° C to 140 ° C with rearrangement and c) obtaining the isomer-enriched mixture having an isomer ratio of at least 80% 3S-caranone or 3R-caranone (based on total amount of 3S and 3R-caranone).
• a reaction mixture containing 3-caranepoxide, at least one acidic catalyst and, in a preferred embodiment, at least one first organic solvent preferably corresponds to a mixing of 3-caranepoxide, at least one acidic catalyst and, optionally, at least one first organic solvent.
• the isomeric mixture may preferably be purified or isolated.
• the at least one acidic catalyst is a Lewis acid, more preferably a metal salt of very strong acids, in particular a metal salt of acids stronger than trifluoroacetic acids having a pKa of 0.23, preferably with metals of the third to fifth period, especially groups 4 to 13, in particular of groups 7 to 12, in particular with an oxidation state of 2 to 3.
• the at least one first organic solvent is an aliphatic or aromatic solvent, in particular a solvent consisting only of hydrocarbons without heteroatoms, in particular a solvent having 4-10 carbons, especially 5-7 carbons, and a boiling point between 30 ° C and 126 ° C. , preferably 60 ° C to 81 ° C, especially with a relative polarity less than 0.164 (dioxane).
• the invention provides that the reaction of the 3-caranepoxide in process step b) to the isomer-enriched mixture of S- and R-caranone at a temperature of 0 ° C to 100 ° C, preferably from 20 ° C to 80 ° C.
• the reaction of the 3-caranepoxide in process step b) takes place under Meinwald rearrangement.
• the Meinwald rearrangement will proceed via a concerted mechanism without intermediates or through an intermediate mechanism, in particular via the intermediates (1R, 6S) -7,7-dimethyl-4-methylenebicyclo [4.1.0] heptane -3-ol and (IR, 6S) -4,7,7-trimethyl-bicyclo [4.l.0] hept-3-en-3-ol.
• the isomer-enriched mixture obtained in process step c) has an isomer ratio of at least 85%, at least 90% or at least 95% 3S-caranone or 3R-caranone (based on total amount of caranone).
• the preparation of intermediates, in particular isomers of 3-caranone, is advantageously made possible, from which the monomers according to the invention required for the polyamide preparation can be obtained.
• the reaction can be controlled in a preferred embodiment such that the corresponding desired intermediate is present in a high proportion in the isomer-enriched mixture obtained, ie either 3S-caranone or 3R-caranone.
• the monomers required for the preparation of the polyamides according to the invention can be prepared inexpensively, quickly and efficiently from this isomer-enriched mixture of 3S-caranone and 3R-caranone via the further intermediates 3-caranoxime and 3-caranlactam.
• the terpene-based, thermoplastic polyamides according to the invention which can be prepared from them satisfy high thermal requirements and have high molar masses.
• the efficiency of the manufacturing process for the Polymers according to the invention are potentially comparable to the commercially used production processes for fossil-based polyamides.
• the production process according to the invention here also referred to as the synthesis route, is preferably controllable in such a way that either a partially crystalline or a completely amorphous polyamide is formed.
• 3-carene-based lactams ie the monomers of the polyamides according to the invention, can be prepared separately in two diastereomers which either lead to complete amorphicity or partial crystallinity in the polyamide and thus fulfill different application requirements.
• a polyamide of 3S-caranlactam is partially crystalline and a polyamide of 3R-caranlactam is amorphous. Both polyamides can reach molecular weights above 50 kDa or (hereinafter abbreviated as "or") 100 kDa, preferably above 10 kDa or 33 kDa.
• the polyamides provided according to the invention preferably have a high optical purity, are transparent in a preferred embodiment and preferably have stereoregularity, which can be advantageously used in particular for stereo and enantioselective applications, for example for chiral stationary phases in HPLC or chiral membranes.
• the polyamides provided according to the invention are isotactic in a preferred embodiment in the form of their homopolymers.
• 3-carene means both (1S, 6R) - (+) - 3-carene and the isomer (IR, 6S) - (-) - 3-carene.
• the substances and products produced according to the invention from the 3-carene have either the stereoisomeric (IS, 6R) (+) configuration or the (1R, 6S) - (-) configuration, preferably the (1S, 6R) - ( +) - Configuration.
• amorphous polymer is understood to mean a polymer in which, by differential scanning calorimetry (DSC) according to method (3) given below, a glass transition point but no melting point is observed up to the decomposition temperature alone or, according to methods (3.1) and (3.2) given below, a glass transition point but no melting point can be observed up to a temperature of 320 ° C (Method 3.1) or to the decomposition temperature (Method 3.2).
• the term "semicrystalline polymer” is understood to mean a polymer in which differential scanning calorimetry (DSC) according to the method (3) given below or in the thermal analysis Methods (3.1) or (3.2) up to the decomposition temperature both a glass transition point and a melting point can be observed.
• DSC differential scanning calorimetry
• the number average (Mn) and weight average (Mw) are preferably determined according to the invention according to the following methods (4.1) or (4.2), in particular according to method (4.2).
• polydispersity is the quotient weight average (also referred to as mass average) (Mw) divided by number average (Mn) understood (Mw / Mn), where (Mn) and (Mw) according to method (4.1) or ( 4.2), in particular according to method (4.2).
• water absorption is understood to mean a mass increase of a polyamide sample after conditioning with water which is reduced in qualitative comparison to PA6 (polyamide 6) compared to the dry state, which is qualitatively compared according to the method (5) given below can be determined to PA6.
• a polyamide is "transparent" if, in qualitative comparison to PA6 and PA12, colorless-transparent to opaque film can be produced according to method (6) given below.
• intermediate is understood to mean a compound which is obtained from a starting compound, in particular 3-carene or 3-caranepoxide, after carrying out a first process step and in at least one second process step, eg also several process steps , in a final product, in this case in particular 3-caranlactam or its polyamide, is converted.
• an intermediate is in particular 3-caranone and 3-caranoxime, ie precursors for the preparation of 3-caranepoxide to the monomer 3-caranlactam.
• an isomer in the context of the present invention is preferably a diastereomeric compound.
• an "isomer-enriched mixture” of the present invention has at least 80, at least 85, at least 90, at least 95, at least 98, at least 99% (based in each case on the amount of isomers of all isomers) of an isomer, especially one the diastereomeric compounds.
• the expression "isomerically enriched mixture of 3S-caranone and 3R-caranone” (also referred to as a 3S- or 3R-caranone enriched mixture or isomer mixture in relation to a specified enrichment) is understood to mean that said isomer-enriched mixture is that mentioned diastereomeric compounds, in particular mainly comprises, in particular to 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% (based on dry mass of the substance diastereomeric compounds to dry mass substance of the mixture), in particular consists of the diastereomeric compounds.
• the term "enriched mixture of” means that the respectively indicated isomers are mainly present in the mixture, preferably 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% by weight (in each case based on mass-dry substance of the diastereomeric compounds to dry substance of the mixture), in particular consists of said diastereomeric compounds.
• the desired isomer can be obtained in high yield and high purity of at least 80%, in particular at least 85%, preferably at least 90%, in particular at least 95%, in particular at least 91% of an isomer (in each case based on molar amount of both isomers) are obtained, in particular without significant proportion of by-products, in particular by-products, which can not be converted or isomerized into the desired isomer.
• the isomer mixture enriched in 3S-caranone can be obtained in only a single reaction step, starting from the epoxide, without necessary intermediate steps.
• the polyamides according to the invention synthesized from 3-carene additionally have a significantly higher glass transition point Tg of 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 ca. 115 ° C, rather than about 60 ° C as with most commercial polyamides from renewable resources.
• the 3R-polycaranamide (also referred to as 3R-polyamide) according to the invention which can preferably be prepared selectively from R-caranlactam is amorphous, preferably completely amorphous, and has a glass transition point Tg of about 100 to 130 ° C., in particular 105 to 125 ° C., in particular 110 to 120 ° C, on.
• Tg glass transition point
• inventive 3S-polycaranamide - with inverted new stereocenter - is partially crystalline with a melting point Tm in the range of 230 to 290 ° C, especially 240 to 285 ° C, especially 260 ° C to 290 ° C, wherein the glass transition point is also in the range of 100 to 130 ° C, in particular 105 to 125 ° C, in particular 110 to 120 ° C.
• Tm melting point
• Tm melting point in the range of 230 to 290 ° C
• 240 to 285 ° C especially 260 ° C to 290 ° C
• the glass transition point is also in the range of 100 to 130 ° C, in particular 105 to 125 ° C, in particular 110 to 120 ° C.
• the crystalline structures present next to the amorphous regions in the molecule allow use at further elevated temperatures.
• the 3S-caranlactam according to the invention is further characterized in a preferred embodiment in that the 3S-caranlactam can be co-polymerized with other lactams, preferably caprolactam (CL) or laurolactam (LL).
• 3S-Caranlactam is preferably at least 1%, in particular at least 10%, in particular at least 50%, in particular at least 70%, in particular at least 80% and up to 100% of the maximum value determined by the quantitative ratio of the monomers at the beginning of the polymerization incorporated into the co-polycaranamide.
• the invention therefore also relates to 3S-co-polycaranamides prepared or preparable from 3S-caranlactam and at least one other lactam, preferably 3R-caranlactam, caprolactam and / or laurolactam.
• 3S-caranlactam-laurolactam-co-polycaranamides according to the invention are characterized in a preferred embodiment in that amorphous phases are formed with increasing incorporation of 3S-caranlactam. This allows adjustment of the crystallinity.
• 3S-caranlactam-laurolactam-co-polycaranamides are characterized in that higher T g can be achieved with increasing incorporation of 3S-caranlactam. This allows the use of higher temperatures compared to PA12 (polyamide 12).
• 3S-Caranlactam-caprolactam-co-polycaranamides according to the invention are preferably characterized in that amorphous phases are formed with increasing incorporation of 3S-caranlactam. This allows adjustment of the crystallinity.
• 3S-caranlactam-laurolactam-co-polycaranamides are characterized in that higher T g can be achieved with increasing incorporation of 3S-caranlactam. This allows the use of higher temperatures compared to PA6.
• the 3R-caranlactam according to the invention is further characterized in a preferred embodiment in that the 3R-caranlactam can be co-polymerized with other lactams, preferably caprolactam or laurolactam.
• 3R-Caranlactam is thereby preferably at least 1.0%, in particular at least 10%, in particular at least 50%, in particular at least 70%, in particular at least 80% and up to 100% of the defined by the quantitative ratio of the monomers at the beginning of the polymerization Maximum value incorporated in the co-polycaranamide.
• the present invention therefore also relates to 3R-co-polycaranamides prepared or preparable from 3R-caranlactam and at least one other lactam, preferably 3S-caranlactam, caprolactam and / or laurolactam.
• 3R-caranlactam-laurolactam-co-polycaranamides according to the invention are characterized in a preferred embodiment in that amorphous phases are formed with increasing incorporation of 3R-caranlactam. This allows adjustment of the crystallinity.
• 3S-caranlactam-laurolactam-co-polycaranamides are more preferred Embodiment characterized in that with increasing incorporation of 3R-caranlactam higher T g can be achieved. This allows the use of higher temperatures compared to PA12.
• Inventive 3R-caranlactam-caprolactam-co-polycaranamides are characterized in a preferred embodiment characterized in that amorphous phases are pronounced with increasing incorporation of 3R-caranlactam. This allows adjustment of the crystallinity.
• 3R-caranlactam-laurolactam-co-Polycaranyamide are characterized in a preferred embodiment characterized in that with increasing incorporation of 3R-caranlactam higher T g can be achieved. This allows the use of higher temperatures compared to P A6.
• Table 1a Properties of a 3S-polycaranamide, a 3R-polycaranamide, a 3S-caranlactam-3R-caranlactam-co-polycaranamide, a 3S-caranlactam-laurolactam-co-polycaranamide and a 3S-caranlactam-caprolactam co-polycaranamide present invention (according to methods (3.1), (3.2) and (4.2)). Further characterization of the polyamides according to the invention can be found in the respective GPC curve for 3S-polycaranamide (FIG. 78), for 3R-polycaranamide (FIG. 79) and for 3R / 3S-co-polycaranamide (FIG. 80).
• Table lb Properties of a 3S-polycaranamide, a 3R-polycaranamide and a 3S-caranlactam-3R-caranlactam-co-polycaranamide according to the present invention (according to methods (3) and (4.1)).
• a further characterization of the polyamides according to the invention can be found in the respective GPC curves for 3S-polycaranamide (FIGS. 51-60), for 3R-polycaranamide (FIGS. 62-71) and for 3S / 3R-co-polycaranamide (FIG. 72), for 3S Caranlactam-laurolactam-co-polycaranamide ( Figures 73-75) and for 3S-caranlactam-caranlactam-co-polycaranamide ( Figures 76-77).
• the 3S-polycaranamide according to the invention (also referred to as 3S-polyamide) is characterized in a preferred embodiment in that the 3S-polycaranamide has a glass transition point (Tg) of 100 ° C to 130 ° C, in particular 105 ° C to 125 ° C, in particular 110 ° C to 120 ° C, a melting temperature or melting range of (Tm) 230 to 300 ° C, in particular 230 to 290 ° C, in particular 250 ° C to 300 ° C, in particular 255 ° C to 295 ° C.
• Tg glass transition point
• Tm melting temperature or melting range
• Mn number average molecular weight
• Mw weight average molecular weight
• the 3S-polycaraneamide according to the invention (also referred to as 3S-polyamide) is preferably characterized in that the 3S-polycaranamide has a glass transition point or glass transition range (Tg) of 100 ° C. to 130 ° C., in particular 105 ° C. to 125 ° C.
• Tg glass transition point or glass transition range
• the 3S-polycaranamide according to the invention is preparable according to one of the methods of the present invention. Furthermore, in a preferred embodiment, the 3S-polycaranamide according to the invention, in a preferred embodiment after polymerization by anionic ring-opening polymerization, in particular according to working examples 7.1.1 - 7.1.11, 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.
• PD polydispersity
• the 3R-polycaranamide according to the invention is preferably characterized in that the 3R-polycaranamide has a glass transition point (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, a number average molecular weight (Mn) of 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 of Molar mass (Mw) of 0.1 -10 5 g / mol to 2, 1 - 10 5 g / mol, in particular 1.1 TO 5 g / mol, (Mn and Mw measured by method (4.1)).
• Tg glass transition point
• Mn number average molecular weight
• Mw weight average of Molar mass
• the 3R-polycaranamide according to the invention is preferably characterized in that the 3R-polycaranamide has a glass transition point (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, a number average molecular weight (Mn) of 1.0 kDa to 100 kDa, in particular 10 kDa to 70 kDa and, in a preferred embodiment, a weight average molecular weight (Mw) of 1.0 kDa to 200 kDa, in particular 15 kDa to 110 kDa (Mn and Mw measured by method (4.2)).
• Tg glass transition point
• Mn number average molecular weight
• Mw weight average molecular weight
• the 3R-polycaranamide of the invention is preparable according to any of the methods of the present invention.
• a 3R-polycaranyamide according to the invention in a preferred embodiment after polymerization by anionic Ringöffhungspolymerisation, in particular according to embodiment 7.2.1 - 7.2.10, a polydispersity (PD) of 1.0 to 10, especially 1.0 to 5, in particular 1.0 to 2.5, in particular 1.0 to 1.3.
• PD polydispersity
• the 3S / 3R co-polyamide according to the invention is preferably characterized in that the 3S / 3R polyamide has a glass transition point (Tg) of 100 ° C to 130 ° C , in particular from 105 ° C. to 125 ° C., in particular from 110 ° C. to 120 ° C., has a melting range from 250 ° C. to 300 ° C., in particular from 255 ° C. to 295 ° C., in particular from 260 ° C. to 290 ° C.
• Tg glass transition point
• Mn number average molecular weight
• Mw mass average molecular weight
• the 3S / 3R co-polyamide according to the invention is preferably characterized in that the 3S / 3R polyamide has a glass transition point (Tg) of 100 ° C to 130 ° C , in particular from 105 ° C. to 125 ° C., in particular from 110 ° C. to 120 ° C., has a melting range from 250 ° C. to 300 ° C., in particular from 255 ° C. to 295 ° C., in particular from 260 ° C. to 290 ° C.
• Tg glass transition point
• Mn number average molecular weight
• Mw weight average molecular weight
• the 3S-caranlactam-3R-caranlactam-co-polycaranamide of the invention is preparable according to any of the methods of the present invention.
• an inventive 3S-caranlactam-3R-caranlactam-co-polycaranamide in a preferred embodiment after polymerization by anionic Ringöffhungspolymerisation, in particular according to Example 7.3.2, 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.
• T g glass transition
• T g glass transition point
• a 3S-caranlactam-laurinlactam-co-polycaranamide according to the invention in a preferred embodiment after polymerization by anionic ring-opening polymerization, in particular according to Example 8.1.1 - 8.1.3, 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.
• PD polydispersity
• T g glass transition point
• a 3S-caranlactam-capro-co-polycaranamide according to the invention has, in a preferred embodiment, after polymerization by anionic ring-opening polymerization, in particular according to Example 8.1.1 - 8.1.3, 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.
• PD polydispersity
• a first isomer of the lactam according to the invention which can be implemented due to its stereochemistry to a predominantly amorphous polyamide and a second Isomer of the lactam according to the invention, the polyamide is semicrystalline to synthesize, both polyamides glass transition points in the range of 100 ° C to 130 ° C, in particular 110 ° C, wherein the 3S-caranlactam to a partially crystalline polyamide and the 3R-caranlactam to an amorphous polyamide can be implemented.
• the procedure according to the invention makes it possible to adjust the crystallinity of polyamides in a targeted manner and to provide isomer-enriched 3-caranlactam and polyamides based thereon with high optical purity.
• the scope of the due to their chemical stability valuable polymer class of polyamides can be further increased.
• Analogous to PA66 mechanically and thermally stressed components such as bobbins, drill housing, automotive oil sump, etc. can be realized, as well as due to the higher temperature stability, applications over 100 ° C permanently possible.
• the fully amorphous polyamide also offers applications in the field of transparent plastics. Combinations of the mentioned applications are also possible, whereby the field of application of the previously known bio-based polyamides in this regard can be significantly extended by the polyamides according to the invention.
• the invention provides polyamides which are in particular designed as 3S-polycaranamide, as 3R-polycaranamide, as 3S / 3R-co-polycaranamide or as co-polycaranamide composed of at least one of the inventive caranlactams and at least one further other lactam.
• polyamides according to the invention which comprise monomers according to the invention may accordingly also be present as co-polycaranamides (in short: co-polyamides).
• the invention therefore also relates to plastic parts which can be produced or produced from polyamides according to the invention, in particular those which consist of or contain the polyamides according to the invention, in particular contain substantial proportions of the polyamides, for example more than 5%, 10%, 15%, 20%, respectively. 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% (based on the total weight of the plastic part).
• the 3-caranepoxide 3S-caranepoxide used in process step a) and the isomer-enriched mixture obtained in process step c) comprise a 3S-caranone-enriched mixture having an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95%, 3S-caranone (based on total amount of carbanone, so 3R and 3S-caranone) is.
• the 3-caranepoxide 3R-caranepoxide used in process step a) and the isomer-enriched mixture obtained in process step c) enrich a 3R-caranone enriched mixture having an isomer ratio of at least 80%, in particular at least 85%, at least 90 % or at least 95%, 3R-caranone (based on total amount of caranol).
• the acidic catalyst is a Lewis acid or a Bronsted acid or a mixture of the Lewis acid and Bronsted acid.
• the acidic catalyst is a strong Bronsted acid or a Bronsted acid with a pKa of at most 0.7.
• the acidic catalyst is a Bronsted acid having a pKa of at most 0.7, such as sulfonic acids, in particular para-toluenesulfonic acid (PTSA), methanesulfonic acid or trifluoromethanesulfonic acid.
• sulfonic acids in particular para-toluenesulfonic acid (PTSA), methanesulfonic acid or trifluoromethanesulfonic acid.
• the acidic catalyst is a sulfonic acid.
• the acidic catalyst is a Lewis acid with an anion of a strong acid, in particular sulfonic acid or an anion such as chlorate, trifluoromethanesulfonate (OTf) or perchlorate (CIO 4 ).
• the acidic catalyst is an iron-Lewis acid, a nickel-Lewis acid, a copper-Lewis acid, a cobalt-Lewis acid or a zinc-Lewis acid, preferably an iron-Lewis Acid, is.
• the acidic catalyst is a Lewis acid having an anion of, in particular strong, acid or one, in particular strong, Bronstcd acid or one, in particular strong, Bronstcd acid with a pKs of at most 0.7.
• anions of, in particular strong, acids such as sulfonic acids, are used as the anion of the Lewis acids or an anion such as chlorate or perchlorate is used.
• Lewis acids in particular for the iron, nickel, cobalt, copper or zinc Lewis acids, chlorate and / or perchlorate and / or sulfonate is used.
• the Lewis acid used may preferably be Fe (Cl0 4 ) 2 H 0, Ni (Cl0 4 ) 2 , Co (Cl0 4 ) 2 , Cu (Cl0 4 ) 2 or their corresponding flydrates.
• the acidic catalyst is a Lewis acid, in particular an iron, copper, cobalt, nickel or zinc Lewis acid, preferably an iron-Lewis acid, with an anion of an especially strong acid
• a trifluoromethanesulfonate or perchlorate, or a strong Bronsted acid having a pKa of at most 0.7 such as sulfonic acids, especially para-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, or a mixture of the aforementioned Lewis acids and Bronsted acids.
• the acidic catalyst is a mixture of the aforementioned Lewis acids and Bronsted acids.
• a zeolite in particular ZSM-5, is used as the acidic catalyst.
• This also has the advantage that the zeolite can be added as a separable solid of the reaction mixture and thus can be separated by filtration.
• an acidic heterogeneous catalyst is used as the acidic catalyst in a gas phase rearrangement.
• the first organic solvent provided in a preferred embodiment is a nonpolar solvent or a solvent having a relative polarity of at most 0.310, more preferably at most 0.200, preferably at most 0.100.
• the first organic solvent is a, in particular non-polar, solvent, such as aliphatic or aromatic hydrocarbons, preferably xylene, toluene, cyclohexane, pentane, hexane or heptane.
• the first organic solvent is 2-methyl-tetrahydrofuran, tetrahydrofuran, ethyl acetate, chloroform or dichloromethane.
• the first organic solvent is a solvent having a relative polarity of at most 0.310, in particular at most 0.200, preferably at most 0.100.
• relative polarity is understood to mean a polarity as described in the document “Solvents and Solvent Effects in Organic Chemistry", Christian Reichards, Wiley-VCH Publishers, 3rd ed., 2003.
• the relative polarities for cyclohexane, hexane, heptane and toluene can be found in the table from Example 1.1.
• This has the advantage that at low concentrations both the overall selectivity and the isomer selectivity can be positively influenced.
• the process has a selectivity of at least 80% conversion of 3S-caranepoxide, based on the total amount of a mixture of 3R-caranone and 3S-caranone, of at least 50%, in particular at least 70%, and wherein this mixture from 3R-caranone and 3S-caranone at least 80%, preferably at least 85% 3S-caranone.
• the acidic catalyst is used in the reaction mixture according to process step a) and b) in a concentration of 0.01 mol% to 2.0 mol% with respect to the 3-caranepoxide used.
• the reaction time for 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 10 minutes to 40 minutes.
• the invention relates in a preferred embodiment to a process for preparing an isomer-enriched mixture of 3S-caranone and 3R-caranone from 3S-caranepoxide, comprising the following process steps: a) providing a reaction mixture containing 3S-caranepoxide, at least one acidic catalyst and a first organic solvent, wherein the acidic catalyst is a sulfonic acid or a Lewis acid selected from the group consisting of Fe (C10 4 ) 2 H 2 O, Ni (Cl0 4 ) 2 , Co (Cl0 4 ) 2 , Ni (C10 4 ) 2 or Cu (Cl0 4 ) 2 or a mixture of the aforementioned acids, and wherein the first organic solvent is selected from the group consisting of toluene, cyclohexane, pentane, hexane, heptane, 2-methyl-tetrahydrofuran, tetrahydrofuran, ethyl acetate and dich
• the invention also relates to an aforesaid process for preparing an isomer-enriched mixture of 3S-caranone and 3R-caranone from 3S-caranepoxide, wherein the acidic catalyst is a sulfonic acid selected from the group consisting of para-toluenesulfonic acid (PTSA), methanesulfonic acid and trifluoromethanesulfonic acid ,
• the 3-caranepoxide used in process step a) is obtained in a process step a1) by epoxidation of 3-carene.
• the starting compound used in process step a) is 3S-caranepoxide and in a process step ala) by epoxidation of 3-carene in the presence of a) a peroxide acid, for example dilute peracetic acid or b) a peroxide, for example, H 2 O 2 , and an enzyme is obtained.
• a peroxide acid for example dilute peracetic acid
• a peroxide for example, H 2 O 2
• the enzyme may be, for example, a lipase, for example lipase B, in particular from Candida spec, in particular from Candida antarctica.
• the starting compound used in process step a) is 3R-caranepoxide and obtained in a process step alb) by epoxidation of 3-carene in the presence of N-bromosuccinimide (NBS), optionally additionally in the presence of a base becomes.
• NBS N-bromosuccinimide
• the isomer-enriched mixture obtained in process step c) is purified, in particular is obtained in isolated form, in particular the acid catalyst and / or the first solvent are separated, and / or the mixture optionally further processing , For example, a drying, is subjected.
• 3S-caranone-enriched mixture preferably obtained in process step c) from 3S-carane oxide in at least one second solvent in the presence of a base or a Bronsted acid in a process step d) a 3R-caranone-enriched mixture having 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 on total amount of caranol) isomerized.
• the base is potassium hydroxide or sodium hydroxide, or another strong base. Furthermore, it is preferably provided that the base is an alcoholate, in particular a methanolate.
• the Bronsted acid is a Bronsted acid with a pKa of at most 0.7.
• the Bronsted acid be a strong Bronsted acid.
• the Bronsted acid is aqueous hydrogen chloride, also referred to as aqueous HCl or hydrochloric acid, or sulfuric acid.
• the Bronsted acid is a sulfonic acid.
• the second solvent is an aprotic-polar solvent having a relative polarity of at least 0.200 or a protic-polar solvent having a relative polarity of at least 0.200.
• the aprotic-polar solvent having 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.
• the protic polar solvent having a relative polarity of at least 0.200 is a solvent such as water, alcohol, amine, carboxylic acid or amide.
• the protic polar solvent having a relative polarity of at least 0.200 is an alcohol such as methanol, ethanol, propanol or butanol.
• the reaction time for 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.
• the 3S-caranone-enriched mixture preferably obtained in process step c) from 3S-caranepoxide in at least one second solvent in the presence of a, in particular strong, base or, in particular strong, Bronsted acid with a pKs of at most 0.7 in a process step d) to a 3R-caranone-enriched mixture having 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 (based on the total amount of caranon) is isomerized, wherein the second solvent a aprotic-polar solvent having a relative polarity of at least 0.200 or a protic-polar solvent having a relative polarity of at least 0.200.
• the 3S-caranone-enriched mixture preferably obtained in process step c) from 3S-caranepoxide in at least one second solvent in the presence of a, especially strong, base or, in particular strong, Bronsted 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, in a process step d) to a 3R-caranone-enriched mixture having 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%, of 3R-caranone (relative to the total amount of caranone) isomerized, the second solvent being an aprotic polar solvent having a relative polarity of at least 0.200, selected from the group consisting of tetrahydrofuran, ethy
• an acid in particular a sulfonic acid or a Lewis acid, is used as the acidic catalyst.
• This embodiment has the advantage that, after distillative removal of the solvent, no further acid has to be added for the catalysis of the rearrangement to 3R-caranone.
• the isomer-enriched mixture obtained in process step d), which is subjected to the isomerization process is purified, in particular is obtained in isolated form, in particular the second Solvent and / or the acid or base are separated and / or the mixture is optionally subjected to further process steps, such as drying.
• the isomer-enriched mixture of 3S- and 3R-caranone obtained in process step c) or d) is preferred in a further process step e) in the presence of at least one third organic solvent, a base and a hydroxylamine Hydroxylamine hydrochloride (HONH 2 -HCl) to a 3-caranoxime-enriched mixture having an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95%, 3S or 3R-caranoxime (based on the total amount of caranoxime, ie 3R and 3S-caranoxime) is reacted.
• HONH 2 -HCl hydroxylamine Hydroxylamine hydrochloride
• a 3R-caranone-enriched mixture in process step e) is used, a 3R-caranoxime-enriched mixture is obtained. If a 3S-caranone-enriched mixture obtained in process step c) is used in process step e), a 3S-caranonoxime-enriched mixture is obtained.
• the third organic solvent is an organic solvent such as an ether, nitrile, alcohol, or an aqueous-organic solvent comprising water and one of the aforementioned third organic solvents.
• the ether is tetrahydrofuran or 2-methyl-tetrahydrofuran.
• the nitrile is acetonitrile.
• the alcohol is methanol, ethanol or isopropanol.
• the base is sodium acetate (NaOAc).
• ethers in particular Tetrahydrofuran, 2-methyltetrahydrofuran
• the 3-caranoxime-enriched mixture obtained from this process has the advantage that the desired isomer is present in a high proportion in the mixture, so that, starting from the starting educt, a predominant proportion of the starting educt into the desired product, ie into the desired intermediate for the desired monomer can be converted in high yields.
• the 3-caranoxime-enriched mixture obtained in process step e) is purified, in particular is obtained in isolated form, in particular the third solvent and / or the base and / or hydroxylamine are separated, and / or the mixture is optionally subjected to further process steps, for example drying.
• a 3S-caranoxime-enriched mixture in process step f) is used, a 3S-caranlactam-enriched mixture, in particular 3S-caranlactam is obtained. If a 3R-caranoxime-enriched mixture obtained in process step e) is used in process step f), a 3R-caranlactam-enriched mixture, in particular 3R-caranlactam, is obtained.
• the 3-caranoxime-enriched mixture obtained in process step e) in a further process step fl) to a predetermined temperature and with addition of a base and para-toluenesulfonyl chloride with rearrangement to 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 (based on
• step fl predetermined temperature 0 ° C to 50 ° C, preferably 10 to 40 ° C, preferably 5 ° C to 20 ° C, in particular 10 ° C to 18 ° C.
• the base is an aqueous base.
• the base is a potassium hydroxide or sodium hydroxide solution.
• the rearrangement is a Beckmann rearrangement.
• a base in particular an aqueous base, preferably a potassium hydroxide or sodium hydroxide solution, and para-toluenesulfonyl chloride under Beckmann rearrangement to a 3-caranlactam-
• the 3-caranoxime-enriched mixture obtained in process step e) is heated to a predetermined temperature in a further process step f2) and converted to a 3-caranlactam-enriched mixture by addition of an especially strong Lewis acid with rearrangement with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95%, 3S- or 3R-caranlactam (based on the total amount of caranlactam) is reacted.
• the temperature specified in process step £ 2) is 15 ° C to 100 ° C, preferably 77 ° C to 87 ° C, particularly preferably 82 ° C.
• the temperature is controlled to a boiling temperature of a solvent, wherein the solvent is the solvent in which the 3-caranoxime-enriched mixture obtained in process step e) is dissolved or present.
• a solvent in which the 3-caranoxime-enriched mixture obtained in process step e) is or is present is acetonitrile.
• the Lewis acid is a strong Lewis acid.
• the Lewis acid is In (ClO 4 ) 3 -nH 2 O (indium perchlorate hydrate) and / or Zn (C 10 4 ) 2 -n FLO (zinc perchlorate hydrate).
• the Lewis acid In (CF; iSCL): ⁇ (indium trifluoromethanesulfonate) and / or ZnfCF ⁇ SCh h (zinc trifluoromethanesulfonate) is.
• the rearrangement is a Beckmann rearrangement.
• the 3-caranoxime-enriched mixture obtained in process step e) in a further process step f2) to a temperature of 77 ° C to 87 ° C, in particular 82 ° C, tempered and with the addition of a particularly strong, Lewis acid, such as In (C10 4 ) 3 -n FLO and / or Zn (C10 4 ) 2 n H 2 O, with rearrangement to a 3-caranlactam-enriched mixture having an isomer ratio of at least 80%, in particular at least 85% at least 90% or at least 95%, 3S- or 3R-caranlactam (based on total amount of caranlactam) is reacted, wherein the 3-caranoxime-enriched mixture obtained from process step e) is preferably dissolved or present in acetonitrile.
• a particularly strong, Lewis acid such as In (C10 4 ) 3 -n FLO and / or Zn (C10 4 ) 2 n H 2 O
• the 3-caranlactam-enriched mixture obtained in process step f) is further purified, in particular obtained in isolated form, in particular the base and / or para-toluenesulfonyl chloride are separated, and / or If appropriate, mixture is subjected to further process steps, for example drying.
• 3R-caranlactam is obtained from the 3-caranlactam-enriched mixture obtained in process step f) after separation of 3S-caranlactam, in particular according to process step g) in a process step h), preferably by crystallization, for example by Distillation, in particular fractional distillation.
• the 3S-caranlactam, 3R-caranlactam or a mixture of 3R- and 3S-caranlactam to 3S-polycaranamide, 3R-polycaranamide or 3S / 3R-copolycaranamide is preferably anionic ring-opening polymerization, cationic ring-opening polymerization, hydrolytic polymerization or polycondensation.
• the present invention also relates to a process for preparing a 3-caranoxime-enriched mixture, comprising the process steps a), b), c) according to the invention, in a preferred embodiment including the process steps al), d) or al) and d), wherein the isomer-enriched mixture of 3S- and 3R-caranone obtained in process step c) or d) in a further process step e) in the presence of at least one third organic solvent, a base, and a hydroxylamine, preferably hydroxylamine hydrochloride (HONH2 ⁇ O) to a 3-caranoxime-enriched mixture having a isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95%, 3S or 3R-caranoxime (based on total amount of caranoxime) is reacted.
• HONH2 ⁇ O hydroxylamine hydrochloride
• the third organic solvent is an organic solvent such as an ether, nitrile, alcohol, or an aqueous-organic solvent comprising water and one of the aforementioned third organic solvents.
• the ether is tetrahydrofuran or 2-methyl-tetrahydrofuran.
• the nitrile is acetonitrile.
• the alcohol is methanol, ethanol or isopropanol.
• the base is sodium acetate (NaOAc).
• the present invention also relates to a process for preparing a 3-caranoxime-enriched mixture, comprising the process steps a), b), c) according to the invention, in a preferred embodiment including the process steps al), d) or al) and d), wherein the isomer-enriched mixture of 3S- and 3R-caranone obtained in process step c) or d) in a further process step e) in the presence of at least one third organic solvent selected from the group consisting of ethers, especially tetrahydrofuran, 2-methyl-tetrahydrofuran , Nitrile, in particular acetonitrile, alcohol, in particular methanol, ethanol and isopropanol, or an aqueous-organic solvent comprising water and one of the abovementioned third organic solvents, a base, and a hydroxylamine, preferably hydroxylamine hydrochloride (HONH 2 -HCl) a 3-caranoxime-enriched mixture with an iso
• the present invention also relates to a process for the preparation of a 3-caranlactam-enriched mixture comprising the process steps a), b), c), e) according to the invention, in a preferred embodiment including the process steps al), d) or al) and d), wherein the 3-caranoxime-enriched mixture obtained in process step e) in a further process step f) rearranged to a 3-caranlactam enriched mixture having an isomer ratio of at least 80% 3S- or 3R-caranlactam (based on total amount of caranlactam ) is implemented.
• the 3-caranoxime-enriched mixture obtained in process step e) in a further process step fl) to a predetermined temperature and with the addition of a base and para-toluenesulfonyl chloride under Rearrangement to a 3-caranlactam-enriched mixture having an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95%, 3S or 3R-caranlactam (based on total amount of caranlactam) is reacted.
• the temperature specified in method step fl) is 5 ° C. to 20 ° C., in particular 10 ° C. to 18 ° C.
• the base is an aqueous base.
• the aqueous base is a potassium hydroxide or sodium hydroxide solution.
• the rearrangement is a Beckmann rearrangement.
• step fl 3-caranoxime-enriched mixture in a further process step fl) to a temperature of 5 ° to 20 ° C, in particular 10 ° to 1 8 ° C, tempered and with the addition of a, in particular aqueous, base, in particular potassium hydroxide or sodium hydroxide solution, and para-toluenesulfonyl chloride under rearrangement, in particular Beckmann rearrangement, to a 3-caranlactam-enriched mixture having an isomer ratio of at least 80%. , in particular at least 85%, at least 90% or at least 95%, 3S- or 3R-caranlactam (based on total amount of caranlactam) is reacted.
• aqueous, base in particular potassium hydroxide or sodium hydroxide solution
• para-toluenesulfonyl chloride under rearrangement in particular Beckmann rearrangement
• the 3-caranoxime-enriched mixture obtained in process step e) is heated to a predetermined temperature in a further process step f2) and added with the addition of an especially strong Lewis acid.
• Acid is converted with rearrangement to a 3-caranlactam-enriched mixture having an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95%, 3S or 3R-caranlactam (based on total amount of caranlactam).
• the temperature specified in method step f2) is 15 ° C. to 100 ° C., preferably 77 ° C. to 87 ° C., particularly preferably 82 ° C.
• the temperature is controlled to a boiling temperature of a solvent, wherein the solvent is the solvent in which the 3-caranoxime-enriched mixture obtained in process step e) is dissolved or present. It is preferably provided that a solvent in which the 3-caranoxime-enriched mixture obtained in process step e) is or is present is acetonitrile.
• the Lewis acid is a strong Lewis acid.
• the Lewis acid In (C10 4 ) 3 n H 2 0 and / or a Zh (Oq4) 2 ⁇ h H 2 0 is.
• the Lewis acid is ln (CFSO 3 ) and / or a Zn (CF 3 SO 3 ) 2 .
• the rearrangement is a Beckmann rearrangement.
• the 3-caranoxime-enriched mixture obtained in process step e) in a further process step f2) to a temperature of 77 ° C. to 87 ° C., in particular 82 ° C, tempered and with the addition of a, in particular strong, Lewis acid, such as In (Cl0 4 ) 3 n H 2 0 and / or a Zn (Cl0 4 ) 2 n H 2 0, rearranged to a 3-Caranlactam- enriched Mixture having an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95%, 3S- or 3R-caranlactam (based on total amount of caranlactam) is reacted, wherein preferably from step e) obtained 3-caranoxime-enriched Mixture is dissolved or dissolved in acetonitrile.
• a, in particular strong, Lewis acid such as In (Cl0 4 ) 3 n H 2 0 and / or a Zn (Cl0
• the present invention also relates to a process for the preparation of 3S-caranlactam from 3S-caranone, which process comprises the process steps e) and f) and wherein in process step e) a, preferably obtained by process step c) 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 (based on total amount of carbanane) used and to a 3S-caranoxime enriched mixture with an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95%, of 3S-caranoxime (based on total amount of caranoxime) reacted in process step f) without removal of the solvent from process step e) and without isolation of the caranoxime to a 3S-caranlactam -enriched mixture having an isomer ratio of at least 80%, in particular at least 85%,
• the present invention also relates to a process for the preparation of 3R-caranlactam from 3R-caranone, which process comprises the process steps e) and f) and wherein in process step e) a, preferably obtained by process step d), isomer-enriched mixture of 3S- and 3R-caranone having 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-caranone (based on Total amount of caranone) and to give a 3R-caranoxime-enriched mixture having 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 (based on total amount of caranoxime), in process step f) without removing g of the solvent from process step e
• the present invention also relates to a process for the preparation of 3S-polycaranamide, 3R-polycaranamide or 3S / 3R-co-polycaranamide and the polyamides prepared therewith, wherein, in particular the obtained according to the invention, 3 S -Caranlactam, 3R-caranlactam or a mixture from 3S- and 3R-caranlactam to 3S-polycaranamide, 3R-polycaranamide or 3S / 3R-copolycaranamide in a process step i), preferably by anionic ring-opening polymerization, cationic ring-opening polymerization, hydrolytic polymerization or polycondensation.
• the present invention also relates to a process for preparing 3S-polycaranamide and the polyamides prepared therewith, wherein, in particular the 3S-caranlactam obtained according to the invention to 3S-polycaranamide in a process step i), preferably by anionic ring-opening, cationic
• Ring opening polymerization, hydrolytic polymerization or polycondensation is polymerized.
• the present invention also relates to a 3S polycaranamide.
• the present invention also relates to a process for the preparation of 3R-polycaranamide and the polyamides prepared therewith, wherein, in particular the 3R-caranlactam obtained according to the invention to 3R-polycaranamide in a process step i), preferably by anionic ring-opening, cationic
• Ring opening polymerization, hydrolytic polymerization or polycondensation is polymerized.
• the present invention also relates to a 3R polycaranamide.
• the present invention also relates to a process for the preparation of 3S / 3R-co-polycaranamide and the polyamides prepared therewith, wherein a mixture of 3S- and 3R-caranlactam, in particular a mixture of the inventively obtained 3S- and 3R-caranlactams, to 3S / 3R-copolycaranamide in a process step i), preferably by anionic ring-opening polymerization, cationic ring-opening polymerization, hydrolytic polymerization or polycondensation is polymerized.
• the present invention also relates to a 3S / 3R copolycaranamide.
• the present invention also relates to a process for the preparation of copolyamides and to the copolyamides prepared therewith, wherein the 3S-caranlactam, 3R-caranlactam or a mixture of 3S- and 3R-caranlactam obtained according to the invention with a monomer, such as laurolactam or caprolactam, to a co-polyamide in a process step i2), preferably by anionic ring-opening polymerization, cationic ring-opening polymerization, hydrolytic polymerization or polycondensation, in particular to 3S-caranlactam-laurolactam-co-polycaranamide (3S-caranlactam-laurolactam-co-polyamide ), 3R-caranlactam-laurolactam-co-polycaranamide (3R-caranlactam-laurolactam-co-polyamide), 3S-caranlactam-3R-caran
• the present invention also relates to a process for the preparation of polymers, in particular polyamides, which completely or as a copolymer or as part of a mixture of different polymers or monomers, the inventive 3-caranlactams, in particular 3 S -Polycaranamid and / or 3R-polycaranamide, in particular 3S -Polycaranamid, or their opened amino acids, amino acid esters or amino acid derivatives.
• the present invention also relates to a process for the preparation of 3S-caranlactam from 3-carene, the process comprising the process steps a) to c), e), f) and g), in particular al) to c), e), f ) and g) and wherein in process step a) a 3S-caranepoxide obtained preferably by epoxidation of 3-carene is used, in process step c) a 3S-caranone-enriched mixture having an isomer ratio of at least 80%, in particular at least 85% , at least 90% or at least 95%, of 3S-caranone (based on total amount of caranone), in process step e) to a 3S-caranoxime enriched mixture having an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95%, 3S-caranoxime (based on the total amount of caranoxime), in process step f) to a 3S-car
• 3S-caranlactam in a process step ia), can subsequently be obtained by polymerization, preferably by anionic ring-opening polymerization, cationic ring-opening polymerization, hydrolytic polymerization or polycondensation, 3S-polyaranamide.
• the present invention also relates to a process for the preparation of 3R-caranlactam from 3-carene, the process comprising the process steps a) to c), e), f) and g), in particular al) to c), e), f ) and g), and wherein in step a) a, preferably obtained by epoxidation of 3-carene, 3R-caranepoxide used, in Process step c) a 3R-caranone-enriched mixture having an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% 3R-caranone (based on total amount of carbanane), in process step e) to a 3R-caranoxime Enriched mixture having an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95% 3R-caranoxime (based on the total amount of caranoxime), in process step f) to a 3R-caran
• 3R-caranlactam in a process step ib), can subsequently be obtained by polymerization, preferably by anionic ring-opening polymerization, cationic ring-opening polymerization, hydrolytic polymerization or polycondensation, 3R-polycaranamide.
• the present invention also relates to a process for the preparation of 3R-caranlactam from 3-carene, which process comprises the process steps a) to h), preferably al) to h) and wherein in process step a), preferably by epoxidation of 3 -Caren obtained, 3S-caranepoxide used, in process step c) a 3S-caranone enriched mixture having an isomer ratio of at least 80%, in particular at least 85%, at least 90% or at least 95%, 3S-caranone (based on total amount of caranon) obtained, in process step d) to a 3R-caranone enriched mixture having 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 (based on total amount of carban) isomerized, in process step e) to a 3R-cara
• 3R-caranlactam in a process step ib), can subsequently be obtained by polymerization, preferably by anionic ring-opening polymerization, cationic ring-opening polymerization, hydrolytic polymerization or polycondensation 3R-polycaranamide.
• the present invention also relates to a 3S-caranone, in particular produced or preparable according to one of the inventive methods of the invention, according to the formula:
• the present invention also relates to a 3S-caranoxime, in particular produced or preparable according to one of the inventive methods of the invention, according to the formula:
• the present invention also relates to a 3S-caranlactam, in particular produced or preparable according to one of the inventive methods of the invention, according to the formula:
• the number n means a natural number, in particular a natural number greater than or equal to 2, preferably a natural one Number of 2 to 1,000,000, in particular a natural number of 10 to 10,000, more preferably a natural number of 75 to 2000, in particular from 100 to 1000.
• the numbers a, b and c, in particular a and b each mean a natural number, in particular a natural number greater than or equal to 1, preferably a natural number from 1 to 1000, in particular a natural number of 10 to 50.
• 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 of 1 to 1000, particularly preferably a natural number of 10 to 50.
• the number b is a natural number, in particular a natural number greater than or equal to 1, preferably a natural number of 1 to 1000, particularly preferably a natural number of 10 to 50.
• the number c is a natural number, in particular a natural number greater than or equal to 1, preferably a natural number of 1 to 1000, particularly preferably a natural number of 10 to 50.
• the natural numbers a and b preferably have a ratio of from 1: 100 to 100: 1, preferably from 1:10 to 10: 1, more preferably from 1: 6 to 6: 1.
• the natural numbers a and c preferably have a ratio of from 1: 100 to 100: 1, preferably from 1:10 to 10: 1, more preferably from 1: 6 to 6: 1.
• the natural numbers b and c preferably have a ratio of from 1: 100 to 100: 1, preferably from 1:10 to 10: 1, more preferably from 1: 6 to 6: 1.
• the natural numbers n, a, b and c, in particular a, b and c, in particular a and b, may be the same or different from one another.
• the natural numbers, n, a, b and c are independent of each other.
• the present invention also relates to a 3S-polycaranamide, in particular produced or preparable according to one of the inventive methods of the invention, according to the formula (with n repeating units):
• the 3S-polycaranamide according to the invention consists solely of 3S-polycaranamide repeat units according to the following repeat unit:
• the 3 S-polycaranamide according to the invention has at least 80%, in particular at least 85%, in particular at least 90%, in particular at least
• 3 S-polycaranamide repeating units according to the following repeating unit includes:
• the present invention also relates to a 3R-polycaranamide, in particular produced or preparable according to one of the inventive methods of the invention, according to the formula (with n repeating units):
• inventive 3R-polycaranamide consists solely of 3R-polycaranamide repeat units according to the following repeat unit:
• the 3R-polycaranamide according to the invention 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%, (based on the total number n of repeating units) comprises 3R-polycaranamide repeating units according to the following repeating unit:
• the present invention also relates to a co-polycaranamide prepared or preparable according to a process of the invention, in particular from 3S-caranlaetam, 3R-caranlactam or a mixture of 3S-caranlactam and 3R-caranlactam containing at least one repeat unit of the following formula
• the present invention also relates to a 3S / 3R co-polycaranamide, in particular produced or preparable according to one of the inventive processes of the invention, according to the formula (with a, b and n repeating units):
• the present invention also relates to a co-polycaranamide prepared or preparable by a process according to the invention, in particular from 3S-caranlactam, 3R-caranlactam or a mixture of 3S-caranlactam and 3R-caranlactam, in particular 3S-polycaranamide, with at least one further lactam, wherein the co-polycaranamide at least one incorporated lactam, preferably laurolactam and / or caprolactam, and at least one repeat unit of the formula
• the present invention also relates to a co-polycaranamide prepared or preparable by a process according to the invention, in particular from 3S-caranlactam, 3R-caranlactam or a mixture of 3S-caranlactam and 3R-caranlactam with at least one further lactam, in particular containing at least one of the following repeating units according to one of the following formulas (with a, b and c repeating units):
• A is a repeating unit of the incorporated into the co-polyamide further lactam is meant. It is preferably provided that the lactam is selected from the group consisting of, laurolactam, caprolactam and a mixture of said lactams.
• the present invention also relates to a co-polycaranamide prepared or preparable by a process according to the invention, in particular from 3S-caranlactam or a mixture of 3S-caranlactam and 3R-caranlactam with at least one further lactam, in particular containing at least one of the following repeat units according to one the following formulas (with a, b and c repeating units):
• A is a repeating unit of the incorporated into the co-polyamide further lactam is meant. It is preferably provided that the lactam is selected from the group consisting of, laurolactam, caprolactam and a mixture of said lactams.
• the present invention also relates to a co-polycaranamide prepared or preparable by a process according to the invention, in particular from 3R-caranlactam or a mixture of 3S-caranlactam and 3R-caranlactam with at least one further lactam, in particular containing at least one of the following repeat units according to one the following formulas (with a, b and c repeating units):
• A is a repeating unit of the incorporated into the co-polyamide further lactam is meant.
• the lactam is selected from the group consisting of, laurolactam, caprolactam and a mixture of said lactams.
• the present invention also relates to a 3S-caranlactam-laurolactam-co-polycaranamide (3S-caranlactam-laurolactam-co-polyamide), in particular prepared or preparable by one of the processes of the invention, in particular from 3S-caranlactam and laurolactam, in particular according to of the formula (with a, b and n repeat units):
• the present invention also relates to a 3S-caranlactam-caprolactam-co-polycaranamide (3S-caranlactam-caprolactam-co-polyamide), in particular produced or preparable by one of the inventive processes of the invention, in particular from 3S-caranlactam and caprolactam, in particular according to the formula (with a, b and n repeating units):
• the present invention also relates to a 3R-caranlactam-laurolactam-co-polycaranamide (3R-caranlactam-laurolactam-co-polyamide), in particular prepared or preparable by one of the processes of the invention, in particular from 3R-caranlactam and laurolactam, in particular according to of the formula (with a, b and n repeating units):
• the present invention also relates to a 3R-caranlactam-caprolactam-co-polycaranamide (3R-caranlactam-caprolactam-co-polyamide), in particular prepared or preparable by one of the inventive processes of the invention, in particular from 3R-caranlactam and caprolactam, in particular according to of the formula (with a, b and n repeating units):
• the present invention also relates to a 3S-caranlactam-3R-caranlactam-laurolactam-co-polycaranamide (3S-caranlactam-3R-caranlactam-laurolactam co-polyamide).
• Polyamide in particular produced or producible according to one of the invention
• Process of the invention in particular of 3S-caranlactam, 3R-caranlactam and laurolactam, in particular according to the formula (with a, b, c and n repeating units):
• the present invention also relates to a 3S-caranlactam-3R-caranlactam-caprolactam-co-polycaranamide (3S-caranlactam-3R-caranlactam-caprolactam-co-polyamide), in particular produced or preparable according to one of the inventive processes of the invention, in particular from 3S-caranlactam, 3R-caranlactam and caprolactam, in particular according to the formula (with a, b, c and n repeating units):
• the present invention also relates to products, in particular plastic products, comprising at least one of the polyamides prepared according to the invention, in particular 3S-polycaranamide, 3R-polycaranamide or at least one of the co-polycaranamides provided according to the invention, in particular comprising at least 5% by weight, at least 10% by weight. , at least 15% by weight, at least 20% by weight, at least 30% by weight, at least 40% by weight, at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80 wt .-%, at least 90 wt .-%, at least 95 wt .-% or at least 99 wt .-% of the polyamide, in particular consisting of at least one of these polyamides.
• plastic products are industrial products, medical devices or components.
• the preferred embodiments for process steps al) to i2) disclosed in connection with the process according to the invention for preparing and further reacting the isomer-enriched mixture of 3S-caranone and 3R-caranone are preferred according to the invention also in process steps al) to i2) in the present case for the processes for preparing the 3-caranoxime-enriched mixture, the 3-caranlactam-enriched mixture, the 3S-polycaranamide, the 3R-polycaranamide, 3S / 3R-co- Polycaranamide, 3S-caranlactam-laurolactam-co-polycaranamide (3S-caranlactam-laurolactam-co-polyamide), 3R-caranlactam-laurolactam-co-polycaranamide (3R-caranlactam-laurolactam-co-polyamide), 3S-caranlactam-3R Carbanolactam-lau
• Polycaranamide (3R-caranlactam-laurolactam-co-polyamide), 3S-caranlactam-3R-caranlactam-laurolactam-co-polycaranamide (3S-caranlactam-3R-caranlactam-laurolactam-co-polyamide)
• Polyamide Polyamide
• 3S-caranlactam-caprolactam-co-polycaranamide 3S-caranlactam-caprolactam-co-polyamide
• 3R-caranlactam-caprolactam-co-polycaranamide 3R-caranlactam-caprolactam-co-polyamide
• 3S-caranlactam 3R-caranlactam-caprolactam-co-polycaranamide 3S-caranlactam-3R-caranlactam-caprolactam-co-polyamide
• polymers in particular polyamides, which are completely or as a copolymer or as part of a mixture of different polymers or monomers, the 3-caranlactams or their open amino acids, Aminoklam or amino acid derivatives.
• the present invention also relates to polymers, in particular polyamides, which completely or as a copolymer or as part of a mixture of different polymers or monomers, the inventive 3-caranlactams, in particular 3S-caranlactam or 3R-caranlactam, in particular 3S-caranlactam or their opened amino acids, Aminoklam or Amino acid derivatives, preferably according to the formulas shown here to 3S-caranlactam, 3S-polycaranamide, 3R-polycaranamide and 3S / 3R-co-polycaranamide.
• inventive 3-caranlactams in particular 3S-caranlactam or 3R-caranlactam, in particular 3S-caranlactam or their opened amino acids, Aminoklam or Amino acid derivatives, preferably according to the formulas shown here to 3S-caranlactam, 3S-polycaranamide, 3R-polycaranamide and 3S / 3R
• Example chromatograms of a 3S-caranone isomer-enriched mixture (FIG. 3) and of a 3R-caranone isomer-enriched mixture (FIG. 4) can be found in the correspondingly indicated figures.
• the following Table 3 contains the retention times of all product-relevant compounds:
• a percent isomer ratio between 3S-caranone and 3R-caranone of an isomer-enriched mixture can be determined by comparison (peak area of the product divided by the total peak area of both products) of the peak areas, especially the TIC peak areas ( total ion current, TIC) of the two products 3S-caranone and 3R-caranone at the retention times according to the table "Retention times of all product-relevant compounds".
• the DSC analysis was performed on a DSC-One by Mettler Toledo.
• the evaluation of the measurements was done with the evaluation software STARe (Version: 13.00a (Build69l7) by Mettler Toledo:
• Cooling I 350 (until -20 C
• DSC analysis Method (3.1) (DSC, Differential Scanning Calorimetry) The DSC analysis according to method (3.1) was carried out on a DSC 1 from Mettler Toledo with the software STARe V. 16.00. Samples (5-10 mg) were measured in aluminum crucibles under nitrogen atmosphere. Method (3.1) was used for analysis of 3S polycaranamides. The corresponding figures 35-50 show segment 10.
• DSC analysis, method (3.2) DSC, Differential Scanning Calorimetry
• the DSC analysis according to method (3.2) was carried out on a DSC 1 from Mettler Toledo using the software STARe V. 16.00. Samples (5-10 mg) were measured in aluminum crucibles under nitrogen atmosphere. Method (3.2) was used for 3R-polycaranamides, 3S-caranlactam-3R-caranlactam-co-polycaranamides, 3S-caranlactam-laurolactam-co-polyamides and 3S-caranlactam-caprolactam co-polyamides.
• the corresponding figures 35-50 show segments 6 and 7. Segment Temperature [° C] Heating rate [K / min] N 2 [mL / min]
• Table 5.2 GPC analysis specification Method (4.2) GPC spectra of the polymers 3S-polycaranamide ( Figure 51 through Figure 61 inclusive), 3R-polycaranamide ( Figures 62 through 71 inclusive), 3S / 3R-co-polycaranamide (FIG 72), 3S-caranlactam-laurolactam-co-polycaranamide (FIG. 73, FIG. 74 and FIG. 75) and 3S-caranlactam-caprolactam-co-polycaranamide (FIG. 76 and FIG. 77) can be found in the correspondingly indicated figures. Determination of water absorption in a qualitative comparison to PA6, method (5)
• PA6 was prepared by anionic ring-opening polymerization (2.8 mmole caprolactam, 0.1 mmole NaH 60% on paraffin wax, 0.05 mmole Ac 2 O, 180 ° C). Residual monomer was removed by refluxing in water / ethanol. 30-42 mg of the PA6 (three samples) and at least two samples of polyamide according to the invention were tempered in the DSC (same apparatus as described in DSC analysis method (3)) for three minutes at 230 ° C., thereby obtaining uniform polyamide. made of blocks. The masses were determined on an OHAUS Discovery DV215CD balance with a maximum error of 0.01 mg. The samples were then each stirred at 25 ° C for three days in water.
• PA6 and PA12 were dissolved in HFIP (25 mg / mL) and transferred to crystallizing dishes (diameter 4 to 12 cm) or coated on PTFE film. After evaporation of the solvent and drying at 85 ° C for at least three hours. White, opaque films were obtained and the qualitative transparency of the polymers according to the invention was determined by visual comparison.
• Exemplary embodiment 1 (method steps a), b) and c)):
• FIG. 4 shows the GC chromatogram of a 3S-caranone isomer-enriched mixture.
• Figure 5 shows the 1H-NMR of 3S-caranone (in pure form) and
• Figure 6 shows the 13C-NMR of 3S-caranone (in pure form).
• Embodiment 1.1
• Table 6 Influence of solvent polarity on the rearrangement of 3S-caranepoxide to a 3S-caranone and 3R-caranone enriched mixture. All experiments were carried out with a concentration of 1 M 3S-caranepoxide at 25 ° C and 0.2 mol% Fe (Cl0 4 ) 2 H 2 O for 8 h. The conversion of 3S-caranepoxide was 100%. Values refer to the TIC area of the GCMS spectrum (uncorrected values).
• Table 7 Comparison of Fe and Zn Lewis acids at 60 ° C in cyclohexane with a concentration of 1 M 3S-caranepoxide and 0.2% catalyst (mol%). Values refer to the TIC area of the GCMS spectrum (uncorrected values).
• Table 8 Reaction under Meinwald rearrangement of 3S-caranepoxide to a 3S-caranone and 3R-caranone enriched mixture with various sulfonic acids as acidic catalyst.
• the values according to Table 4 refer to the TIC area of the GCMS spectrum (uncorrected values).
• Embodiment 1.3
• Table 10 Influence of the concentration of 3S-caranepoxide on the rearrangement of 3S-caranepoxide to a 3S-caranone and 3R-caranone enriched mixture. All experiments were carried out at 25 ° C and 0.2% Fe (Cl0 4 ) 2 H 2 O for 7 h. Values refer to the TIC area of the GCMS spectrum (uncorrected values). All experiments were performed in cyclohexane.
• Exemplary embodiment 1.5
• Table 11 Temperature influence of Lewis acids on the Meinwald rearrangement of 3S-caranepoxide. Values refer to the TIC area of the GCMS spectrum (uncorrected values).
• Embodiment 1.6
• FIG. 4 shows the GC chromatogram of a 3R-caranone isomer-enriched mixture.
• Figure 5 shows the 1H-NMR of 3S-caranone (in pure form) and
• Figure 6 shows the 13C-NMR of 3S-caranone (in pure form).
• Exemplary embodiment 2.2 (method step d)):
• Table 12 Influence of the solvent on the isomerization of a 3S-caranone-enriched mixture (purity 79%, 3S-caranone 89%, 3R-caranone 11%). All experiments were carried out with a concentration of 1 M 3S-caranone and 2 M HCl solution as isomerization catalyst. Samples were taken after six hours at room temperature (a), another 15 hours at room temperature (b) and another 48 hours at 60 ° C (c) stirring. Values refer to the TIC area of the GCMS spectrum (uncorrected values).
• Exemplary embodiment 3.1 (method step ala):
• FIG. 7 shows the 1H-NMR of 3S-caranoxime (in pure form) and FIG. 8 shows the 13C-NMR of 3S-caranoxime (in pure form).
• Exemplary embodiment 4.2 (method step e)):
• reaction mixture from Example 4.1 (step e)) is cooled to 15 ° C and slowly 4 eq NaOH are added as 10 M NaOH. After two hours of stirring at 15 ° C 1 eq para-toluenesulfonyl chloride is added in portions and stirred for a further two hours at room temperature. The aqueous phase is separated off and extracted with ethyl acetate (twice by volume). The organic phases are washed with half-saturated sodium bicarbonate solution (2 ⁇ ) and then with saturated sodium chloride solution.
• FIG. 9 shows the 1H-NMR of 3S-caranlactam (in pure form) and FIG. 10 shows the 13C-NMR of 3S-caranlactam (in pure form).
• Exemplary embodiment 5.2 (method steps e) and f)):
• reaction mixture from embodiment 5 (process step f)) is fractionally distilled until almost complete crystallization of 3S-caranlactam.
• the remaining portion of 3R-caranlactam can not crystallize under the reaction conditions and thus becomes by a further distillation step (step h)), so that the 3S-caranlactam is obtained. From the distillation mentioned can be obtained as distillate, the 3R-caranlactam.
• Exemplary embodiment 6.2 (method steps g) and h)):
• the 3R-caranlactam could be obtained from the mother liquor (remaining solution from Example 6.1) of the synthesis of 3S-caranlactam after distillation (b.p .: 350 ° C.) and repeated recrystallization (ethyl acetate) as pure product.
• Exemplary embodiment 7.1 (method step i)):
• Exemplary embodiment 7.1.3 (method step i)):
• Exemplary embodiment 7.1.9 (method step i)):
• Exemplary embodiment 7.2 (method step i)):
• Exemplary embodiment 7.3 (method step i)):
• Exemplary embodiment 8 (method step i2)):
• Exemplary embodiment 8.1.3 (method step i2)):
• Exemplary embodiment 8.2.1 (method step i2)): Polymerization of 3S-caranlactam and caprolactam to a 3S-caranlactam-caprolactam-co-polycaranamide
• Exemplary embodiment 9 (method step i2)):
• caprolactam 44 mmol
• 3S-caranlactam 15 mmol
• 75 mg of N-benzoyl-3S-caranlactam IUPAC: (IR, 5S, 7S) -4-benzoyl-5,8,8-trimethyl-4-azabicyclo [5.lO] octan-3-one
• 50 mg NaH 60% added to paraffin wax.
• the temperature of 190 ° C was maintained for 30 min and then cooled to room temperature without active cooling.
• the resulting polymer was crushed and stirred in an ethanol-water mixture (1: 1) for 24 h at reflux temperature. After filtration, the resulting polymer was dried at 120 ° C for 16 h.
• Exemplary embodiment 10 Water absorption of a 3R polyamide
• PA6 was prepared by anionic ring-opening polymerization (2.8 mmol caprolactam, 0.1 mmol NaH 60% on paraffin wax, 0.05 mmol Ac 2 O, 180 ° C). Residual monomer was removed by refluxing in water / ethanol. 30-42 mg of PA6 (three samples) and two samples of poly-3R-caranamide were annealed in the DSC (same apparatus as described in DSC Analytical Method (3)) for three minutes at 230 ° C and thus uniform Polyamide blocks produced. The masses were determined on an OHAUS Discovery DV215CD balance with a maximum error of 0.01 mg. The samples were then each stirred at 25 ° C for three days in water.
• Exemplary embodiment 11.1 Qualitative measurement of the transparency of 3R polyamide compared to PA6 and PA12
• 3R polyamide was dissolved in HFIP (25 mg / mL) and applied to a PTFE film by gentle dripping. After evaporating the solvent and drying at 85 ° C for three hours, a transparent film with defects due to uneven evaporation and air pockets was obtained as compared with PA6 and PA12.
• Exemplary embodiment 11.2 Qualitative measurement of the transparency of amorphous 3S-caranlactam-laurolactam-co-polycaranamide in comparison to PA6 and PA12
• Amorphous 3S-caranlactam-laurolactam-co-polycaranamide was dissolved in HFIP (25 mg / ml) and transferred to a crystallizing dish (diameter 9 cm). After evaporating the solvent and drying at 85 ° C for three hours, a transparent film with defects due to uneven evaporation and air pockets was obtained as compared with PA6 and PA12.
• Exemplary embodiment 11.3 Qualitative measurement of the transparency of amorphous 3S-caranlactam-caprolactam-co-polycaranamide in comparison to PA6 and PA12
• Amorphous 3S-caranlactam-caprolactam-co-polycaranamide was dissolved in HFIP (25 mg / mL) and applied to a PTFE film by gentle dripping. After evaporating the solvent and drying at 85 ° C for three hours, a transparent film with defects due to uneven evaporation and air pockets was obtained as compared with PA6 and PA12.

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