Polyamides with cyclic terpenoid substructures

Abstract

The claimed polyamides comprise at least 10% by weight of at least one cyclic terpenoid substructure. The substructure is preferably derived from a monoterpene. Methods for preparing the polyamides and for preparing molding compositions are also described. The molding compounds comprise 10% to 90% by weight of these polyamides.

Description

Technical Field

[0001] The present invention relates to polyamides having cyclic terpenoid substructures. Background Art

[0002] Replacing conventional plastics with plastics that can be produced from renewable raw materials has attracted great attention as a means of saving fossil resources and reducing greenhouse gas emissions. Polyamides can be prepared from the condensation of diamines with dicarboxylic acids and from amino acids or lactams. The amino and carboxyl groups in the latter refer to the coexistence of two functional groups required for the connection in the same molecule.

[0003] Lactams of camphor and menthone are described in the literature (Kumar, Med. Chem. Res. 2012, p. 531). Also known from the literature are lactams from α-pinene and 3-carene (RE Gawley, Org. React. 1988, 35, 1). A publication by Lochinski et al. (Tetrahedron: Asymmetry, 2000, 11, 1295) describes lactams from 3-carene and ring-opened aminocarboxylic acids prepared therefrom.

[0004] CN 107129572 A and Winacker (Chem. Commun. 2018, 841-844) disclose anionic polymerization with the aid of Grignard compounds or sodium hydride and KOtBu.

[0005] DE 102014221061 A1 discloses the use of at least one terpene lactam in the production of polyamides. The present application discloses an embodiment starting from camphor lactam, which should react with ε-caprolactam to form a copolymer. The method uses a certain amount of sodium lactate as a so-called catalyst and a small amount of acyl caprolactam as a so-called activator. The unreacted residual monomers in the resulting polymer are determined. The mass of camphor-based lactam in the residual monomers only slightly exceeds the amount of camphor lactam (including sodium lactam) used. Comparative examples without camphor lactam are not included, and product properties are not disclosed. According to this disclosure, a person skilled in the art must assume that camphor lactam is not involved in polyamide formation at all.

[0006] A similar method for menthone lactam was used using benzoyl chloride and sodium lactamate in a paper published by Winnacker (Macromol Chem. Phys., 2014 (215), 1654-1660: Synthesis of Novel Sustainable Oligoamides via Ring-Opening Polymerization of Lactams Based on (-)-Menthone) using menthone lactam. MALDI-TOF spectroscopy confirmed the formation of low molecular weight oligomers of menthone lactam.

[0007] Winnacker (Macromol. Rapid Commun., 2017 (40) 1800903) discloses the acid-catalyzed formation of (cationic) polyamides from pinene-based ε-lactams. The polymers obtained by hydrolytic polymerization only achieve low molar masses and low yields.

[0008] Stockmann (Macromol. Rapid Commun., 2019 (38) 1600787) disclosed anionic polymerization of lactams based on carene and pinene; the only acid-catalyzed reaction did not produce any product.

[0009] All reaction products according to DE 102014221061 A1 and Winnacker are substituted at the N-terminus by an acyl group; in the case of DE 102014221061 A1, the acyl group originates from the acylcaprolactam used, in the case of the Winnacker process from the benzoyl chloride used.

[0010] Floyd (Reinhold Plastics Applications Series: Polyamide Resins, 2nd edition, 1966, p. 59 / 60) discloses various methods for producing polyamide 6 (nylon-6). In one of these methods, nylon-6,6 salt is included in the list of initiators. No purpose or result of this use is disclosed.

[0011] Floyd further discloses in the section on nylon-6 (page 9 of the above reference) that when polyamide 6 is produced continuously, the product has a monomer content of about 10%. This monomer acts as a plasticizer and changes the mechanical properties of the product so that it cannot be used in this form. The residual monomer content can be reduced by selecting other process steps.

[0012] EP 3143069 A1 discloses disadvantages such as low molar mass and low viscosity in polyamides caused by excessively high residual monomer contents.

[0013] The problem addressed by the present invention is therefore to provide polyamides containing cyclic terpenoid substructures, the range of which is limited by the nitrogen atoms of the amide group. Summary of the invention

[0014] The present invention provides a method for preparing polyamide, wherein a small amount of a phosphorus-containing acid and a mediator are added.

[0015] The present invention further provides a polyamide comprising at least 10% by weight of at least one cyclic terpenoid substructure, wherein the substructure is preferably derived from a monoterpene producible by the process according to the invention.

[0016] The invention also provides molding compositions which comprise 10 to 90% by weight of at least one polyamide according to the invention.

[0017] The present invention further provides a molded article produced by the molding composition of the present invention. The molded article is preferably a molded article, a film, a bristle, a fiber or a foam. The molded article can be produced, for example, by compression molding, foaming, extrusion, coextrusion, blow molding, 3D blow molding, coextrusion blow molding, coextrusion 3D blow molding, coextrusion suction blow molding or injection molding. These processes are known to those skilled in the art.

[0018] The invention also provides for the use of the moldings of the invention, which can be used, for example, as fiber composite parts, shoe soles, outer coatings for skis or snowboards, dielectric cords, eyeglass frames, design articles, sealing materials, body protection, insulation materials or housing parts with films.

[0019] The polyamide of the present invention, the composition and molding material including the molding material of the present invention, the method of the present invention and the use of the present invention are described below by illustrative embodiments, but the present invention is not limited to any of these illustrative embodiments. When the range, general formula or category of the compound is described below, these include not only the corresponding range or group of the explicitly mentioned compound, but also all sub-ranges and subgroups of the compound that can be obtained by extracting a single value (range) or a compound. In the case of citing documents in the context of this specification, the entire content is intended to be part of the disclosure of the present invention. In the case of the % values ​​given below, unless otherwise stated, these values ​​are weight % values. In the case of the composition, unless otherwise stated, the % value is based on the total composition. Unless otherwise stated, the average value given below is the mass average (weight average). When the measured values ​​are given below, unless otherwise stated, these measured values ​​are measured at a pressure of 101 325Pa and a temperature of 25°C.

[0020] The scope of protection includes the finished and packaged forms of the product according to the invention which are customary in the trade, both as is and in any reduced size form, as long as these are not limited in the claims.

[0021] Optionally, the different units of the polyamide follow a statistical distribution. The statistical distribution is a block-like structure with any desired number of blocks and with any desired order, or they obey a randomized distribution; they can also have an alternating structure or form a gradient on the polymer chain; in particular, they can also form any mixed form, in which groups with different distributions can optionally follow each other. As a result of the embodiment, a specific embodiment can form a restricted statistical distribution. For all regions not affected by this restriction, the statistical distribution remains unchanged.

[0022] One advantage of the polyamides according to the invention is that they are transparent.

[0023] A further advantage of the polyamides according to the invention is that they comprise a considerable mass proportion of renewable raw materials.

[0024] Yet another advantage of the polyamides of the invention is the reduced residual monomer content. This allows further purification steps to be reduced, making the process more efficient.

[0025] Residual monomers within the scope of the present invention are low molecular weight fractions with a molar mass of less than 500 g / mol. The measurement is carried out by GPC as described in the examples. The content values ​​are expressed in % by weight.

[0026] It is known to the person skilled in the art that residual monomers adversely affect the properties of polyamides. These residual monomers can, for example, act as plasticizers, leading to inadequate mechanical properties.

[0027] Another advantage is the adjustability of the properties of the copolyamides based on bicyclic terpene lactams. In particular, the polymerization products of pinene lactams have a particularly high glass transition temperature.

[0028] Monoterpenes are hydrocarbon structures containing 10 carbon atoms known to those skilled in the art. The cyclic terpenoid substructure may optionally contain double bonds. The polyamide of the present invention preferably has a three-membered ring, a four-membered ring and / or a five-membered ring in the cyclic terpenoid substructure. More preferably, the polyamide of the present invention has 10 carbon atoms in its cyclic terpenoid substructure.

[0029] The cyclic terpenoid substructure preferably comprises a ring preferably having two geminal methyl groups. The ring is more preferably 1,1-dimethylcyclopropane, 1,1-dimethylcyclobutane or 1,1-dimethylcyclopentane and optionally mixtures of these rings. The 1,1-dimethyl-substituted ring has substituents only in the α and α' positions, i.e. in the two positions adjacent to the dimethyl-substituted ring member, in the chain forming the polymer, at the ends of which the functional groups for forming amide groups are located. A person skilled in the art will appreciate that the groups whose positions have not yet been defined must be arranged so that the formal cleavage of the substructure claimed results in two formal isoprenoid units.

[0030] The polyamide of the present invention preferably contains 1 to 100 ppm of a phosphorus-containing component; the component may be inorganic or organic in nature, preferably the inorganic component is an inorganic acid, more preferably hypophosphorous acid. More preferably, the polyamide contains 2 to 100 ppm, even more preferably 5 to 60 ppm, wherein the content values ​​are based on the total mass of the polyamide.

[0031] The polyamide of the invention preferably has a residual monomer content of 3% to 20% by weight, preferably 5% to 15% by weight, more preferably 7% to 13% by weight, based on the total mass of the polyamide.

[0032] The polyamide of the invention preferably has a molar mass of at least 3500 g / mol. More preferably, the polyamide has a molar mass of at least 3500 g / mol and a proportion of at least 50% by weight consisting of cyclic terpenoid substructures, wherein the ring has 4 ring members. More preferably, the polyamide comprises at least 60% by weight, in particular at least 70% by weight and not more than 95% by weight, preferably not more than 90% by weight, more preferably not more than 85% by weight of cyclic terpenoid substructures with 4 ring members.

[0033] The polyamide of the invention preferably has a molar mass of at least 8000 g / mol, preferably at least 9000 g / mol, more preferably at least 10000 g / mol. More preferably, the polyamide has a molar mass of at least 8000 g / mol and a proportion of at least 50% by weight consisting of cyclic terpenoid substructures, wherein the ring has 3 ring members. More preferably, the polyamide comprises at least 60% by weight, in particular at least 70% by weight and not more than 95% by weight, preferably not more than 90% by weight, more preferably not more than 85% by weight of cyclic terpenoid substructures with 4 ring members.

[0034] The molar mass in the context of the present invention is the number-average molar mass (Mn) and can be established according to the prior art; the determination of the molar mass is preferably by GPC or by end groups, more preferably by GPC.

[0035] In addition to the cyclic terpenoid substructure, the polyamide of the invention preferably comprises at least one unit of polyamide K, L and / or M, wherein the sum of units consisting of K+L+M is at least 2. Unit K is derived from a diamine, L from a diacid and M from an amino acid. In this case, the polyamide of the invention is a copolyamide.

[0036] The proportion of polyamide structures composed of K, L and / or M is preferably 1% to 90% by weight, preferably 2% to 75% by weight, more preferably 3% to 60% by weight, even more preferably 5% to 50% by weight, particularly preferably 10% to 30% by weight, in particular 15% to 25% by weight.

[0037] The polyamide of the present invention preferably has a glass transition temperature greater than or equal to 100°C, preferably 105°C, more preferably 110°C.

[0038] The polyamide according to the invention preferably has a residual monomer content of less than or equal to 15% by weight, 13% by weight, 12% by weight, 11% by weight and particularly preferably less than or equal to 10% by weight.

[0039] The polyamide according to the invention preferably comprises at least 10 mol % of cyclic terpenoid substructures having a four-membered ring as cyclic terpenoid substructure, the indicated content being based on the total polyamide. The polyamide according to the invention preferably comprises at least 15 mol %, at least 20 mol %, 30 mol %, 40 mol %, 50 mol %, 60 mol %, 70 mol %, 80 mol %, 85 mol %, 90 mol % and particularly preferably 95 mol % of cyclic terpenoid substructures having a four-membered ring.

[0040] The polyamide of the invention comprises at least 10% by weight of at least one cyclic terpenoid substructure, and the polyamide structures K, L and / or M are preferably free of any other polyamide.

[0041] The polyamide of the present invention preferably has repeating units selected from the following cyclic terpene substructures:

[0042]

[0043]

[0044] Preferred substructures are 1c', 1c", 1'c', 1'c", 3c', 3c", 3'c', 3'c", 5c' and 5c".

[0045] Particular preference is given to the substructures 1c', 1c", 3c' and 3c".

[0046] The polyamide of the present invention can be prepared according to the prior art, but is preferably prepared according to the method of the present invention, which comprises the following steps:

[0047] a) providing at least one bicyclic terpene lactam,

[0048] b) ring-opening polymerizing at least one bicyclic terpene lactam to provide a polyamide, preferably a homopolyamide or a copolyamide,

[0049] wherein the phosphorus-containing acid is used in step b) in an amount of 2 to 100 ppm, based on the total mass of the monomers used,

[0050] Therein, a mediator is added in step b).

[0051] In step a), preference is given to bicyclic terpene lactams having a three-membered ring, a four-membered ring or a five-membered ring in addition to the lactam ring.

[0052] Step b) is preferably carried out by adding a phosphorus-containing acid, more preferably hypophosphorous acid. Preferably, an amount of 2-100 ppm, more preferably 10-100 ppm, particularly preferably 20-100 ppm, particularly preferably 30-60 ppm is used. The content values ​​are based on the total mass of the monomers used.

[0053] Step b) is preferably carried out at a "lower" temperature, preferably below 270°C, more preferably below 260°C, 255°C, 250°C, 245°C and at least 240°C.

[0054] The reaction time at a temperature of at least 240° C. in step b) is preferably kept “not too long”, preferably at most 10 hours, 8 hours, 7 hours, 6 hours, 5 hours, 4 hours, at least 2 hours.

[0055] The pressure set at the reaction temperature ("high pressure") in step b) is preferably maintained for 10-90% of the reaction time, after which it is reduced to ambient pressure and maintained at a pressure of 1-1.2 bar for the remaining reaction time. More preferably, the high pressure is maintained for 20-80%, more preferably 30-70%, particularly preferably 40-60%.

[0056] Step b) is preferably carried out using a mediator which is incorporated into the polyamide of the invention during the reaction, and preferably a phosphorus-containing acid is used in an amount of 2 to 100 ppm, based on the total mass of the monomers used.

[0057] Preference is given to using nylon salts or α,ω-amino acids (as intramolecular salts) as mediators. The mediator is preferably used in an amount of not more than 25% by weight, 20% by weight, 15% by weight, 10% by weight, 5% by weight, particularly preferably 5-17% by weight, 8-15% by weight, 9-13% by weight, based on the amount of monomers used, particularly preferably based on the amount of bicyclic terpene lactam used.

[0058] The nylon salt is composed of an α,ω-diammonium compound and an α,ω-dicarboxylate compound, and the nylon salt is preferably an aliphatic type. The diammonium compound is preferably nonlinear, and more preferably the diammonium compound has more than 6 and up to 25 carbon atoms. A diammonium compound having at least one ring structure is preferred. Particularly preferred are diammonium compounds including a PACM (4,4'-methylenebis[cyclohexylamine]) structure. A dicarboxylate compound having more than 6 and up to 25 carbon atoms is preferred. Particularly preferred are diammonium compounds having at least one ring structure and dicarboxylate compounds having more than 6 and up to 25 carbon atoms.

[0059] In the context of the present invention, the term "terpene lactam" is understood to mean a compound having at least one bicyclic ring system, one of the rings containing an amide bond -NH-CO-.

[0060] In all cases where molecules / molecular fragments have one or more stereocenters or can be distinguished into isomers due to symmetry or due to other effects (such as restricted rotation), the present invention encompasses all possible isomers.

[0061] Isomers are known to the person skilled in the art; in particular, reference is made, for example, to the definitions given by Professor Kazmarier of Saarland University, for example in http: / / www.uni-saarland.de / fak8 / kazmaier / PDF_files / vorlesungen / Stereochemie%20Strassb%20Vorlage.pdf. Wherein, in the context of the present invention, reference is made to natural products such as pinene, this is generally to be understood as meaning all isomers, preferably the respective naturally occurring isomers, in the case of α-pinene.

[0062] Natural products are defined by reference to the ranges given in the online version of the Dictionary of Natural Products, Chapman and Hall / CRC Press, Taylor and Francis Group, e.g. from 2018: http: / / dnp.chemnetbase.com / .

[0063] The terpene derivatives may be synthetic or semi-synthetic in nature or they may be isolated as natural products from living organisms of the biosphere or from another source. Preferably the starting material is obtained from the residues of cellulose production and then synthetically converted to the corresponding lactam.

[0064] In particular, all possibilities resulting from stereochemically defined stereoregularity are covered, such as isotactic, syndiotactic, heterotactic, hemi-isotactic, atactic. In the context of the present invention, polyamides having at least partially atactic substituent sequences are preferred.

[0065] Bicyclic terpene lactams have multiple stereocenters.

[0066] Particularly preferred bicyclic terpene lactams have, in addition to the lactam ring, a three-membered ring, a four-membered ring or a five-membered ring.

[0067] The bicyclic terpene lactams are preferably prepared from the corresponding bicyclic terpene ketones.

[0068] The bicyclic terpene ketone is preferably prepared from the corresponding bicyclic monounsaturated terpene or the corresponding bicyclic hydroxylated terpene. Particularly preferably, the ketone is prepared from the following precursor molecules:

[0069]

[0070]

[0071] Particularly preferred bicyclic terpene ketones are:

[0072]

[0073] Particularly preferred bicyclic three-membered ring terpene lactams are:

[0074] Particularly preferred bicyclic four-membered ring terpene lactams are:

[0075]

[0076] Particularly preferred bicyclic five-membered ring terpene lactams are:

[0077]

[0078] Particularly preferred bicyclic terpene lactams are those of the formula:

[0079] 1b', 1b", 1'b', 1'b", 3b', 3b", 3'b', 3'b", 5b' and 5b".

[0080] In the process according to the invention, preferably no metal lactamates are used.

[0081] In the process according to the invention, preferably no N-acyl lactams are used.

[0082] Particular preference is given to not using metal lactamates and N-acyl lactams.

[0083] The polymerization of all lactams and bifunctional compounds provided in step a) is preferably carried out in step b). More preferably, a conversion of at least 95%, preferably at least 90%, particularly preferably at least 85% occurs. The conversion is determined by the residual monomer content in the polyamide according to the invention.

[0084] The invention further provides polyamides prepared by the process according to the invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0085] Figure 1 The influence of temperature on the number-average molar mass (Mn) at a reaction time of 6 h is described for polyamides composed of subbuilding blocks derived from carene. At least 95 mol % of the lactam consists of 3R,4S,6R-carene lactam.

[0086] Figure 2 Describes Figure 1 Effect of temperature on residual monomer content at the 6-hour reaction time. DETAILED DESCRIPTION

[0087] method

[0088] Differential Scanning Calorimetry (DSC):

[0089] Unless otherwise stated, all DSC measurements were performed on a Mettler Toledo DSC1 instrument in an open aluminum crucible. A method is used for polymers in which two heatings are performed. For determining the glass transition temperature, only the second heating curve is used. In this illustration, the first heating curve is shown in black, the cooling curve is shown in red, and the second heating curve is shown in blue. In the case of monomers, heating is usually performed only once.

[0090] Nuclear Magnetic Resonance (NMR):

[0091] all 1 H. 13C{1H}, 13 Both C DEPT-135 and 2D-NMR spectra were recorded on a Bruker Avance III HD 500 instrument. Various solvents were used, with locking at the respective resonances as standards. Signal multiplicities are abbreviated as follows: s: singlet; d: doublet dd: double of doublets; ddd: double of doublets; t: triplet; td: double of triplet; tt: triple of triplet; q: quartet; m: multiplet. 13 The C-DEPT-135 spectrum identified quaternary carbon nuclei, methine, methylene and methyl groups.

[0092] Relative solution viscosity (η rel ):

[0093] The samples were dissolved in m-cresol (0.005 g / ml) at 30° C. and measured at 25.00° C. in a viscosity measuring system (LAUDA PVS or Schott AVS Pro).

[0094] Gel Permeation Chromatography (GPC):

[0095] GPC analysis was performed using an Agilent system of modular construction. This included a pump, autosampler and column assembly (PSG column). The detector used was an RI detector. The sample was dissolved in hexafluoroisopropanol (HFIP) at a concentration of c = 5 g / l, and 0.05 mol / l of potassium trifluoroacetate was added. The measurement was performed with HFIP and 0.05 mol / l potassium trifluoroacetate at a flow rate of 0.8 ml / min using RI detection; relative to the distribution in a narrow range (Mp between 505 g / mol and 4*10 6 g / mol) were used for calibration.

[0096] The alkaline determination of the carboxyl end groups was carried out in benzyl alcohol at 100°C and the alkaline determination of the amino end groups was carried out in m-cresol using a Metrohm 809 Titrando.

[0097] Since the number of end groups is inversely proportional to the length of the chain, the molar mass can be estimated from the determination of the end groups. The end groups are expressed as mmol / kg. These values ​​are used to calculate the number average molar mass according to the following formula:

[0098]

[0099] Gas chromatography (GC) for determination of monomer content:

[0100] Gas chromatography was performed on a dual column system with two separation columns of different polarity. Unless otherwise stated, the samples were dissolved in toluene. Detection was performed with the aid of a flame ionization detector (FID). Evaluation was performed by normalizing the gas chromatographically detectable fractions to 100 area %.

[0101] Gas chromatography-mass spectrometry (GC-MS):

[0102] GC-MS measurements were performed on an Agilent GC 7890 / Agilent MSD 5977 system.

[0103] The separation in the GC / FID analysis is reproduced on a comparable column in a GC system with mass spectrometry detection (GC-MS). The signals are detected chromatographically in a similar manner to the GC / FID analysis. Ionization is performed by electron impact ionization.

[0104] Example 1: General Procedure for Polymerization of Carene Lactam

[0105] 10 g (0.0598 mol) of carene lactam are added to a thick-walled test tube. 30 wt. % water (4.3 ml), 57 ppm of H3PO2 and, if specified, the salts of PACM20 and DDA are added thereto. The test tube is placed in a steel bomb tube equipped with a pressure gauge. The apparatus is tightly closed and purged with nitrogen for 15 minutes. In order to check that the apparatus is airtight, it is then closed with a nitrogen pressure of 1 bar and observed for 5 minutes to see whether the pressure remains stable. The tightly closed steel bomb tube is placed in a metal bath filled with Wood's metal and heated to the reaction temperature within 30 minutes. The temperature and pressure are maintained for half the reaction time. At the end of this time, the apparatus is decompressed to standard pressure within 30 minutes and purged with nitrogen, and the temperature is maintained for the remaining reaction time. The steel bomb tube is then removed from the metal bath and allowed to stand overnight at room temperature in a nitrogen stream.

[0106] Table 1: Reaction conditions and analytical results of Example 1, T = temperature, MAmt = amount of mediator in mol % based on the amount of carene lactam used, Mono = monomer fraction (residual monomer content)

[0107]

[0108] Comparison of experiments C28, C29 and C30 with similar experiments without addition of mediator; C16, C5 and C6 show a significantly reduced residual monomer content. It is also advantageous that at reaction times of 5 and 6 hours, the molar mass is increased by the addition of the mediator.

[0109] The glass transition temperature is related to the molar mass.

[0110] Comparison of reaction times shows that at the same temperature, the molar mass decreases sharply with increasing reaction time. The optimum reaction time decreases with increasing reaction temperature.

[0111] Example 2: General method for the polymerization of pinene lactam

[0112] 10 g (0.0598 mol) of pinene lactam are added to a thick-walled test tube. 35 wt% of water (5.4 ml), 57 ppm of H3PO2 and a mediator (as shown in Table 2) are added thereto, and the test tube is placed in a steel bomb tube equipped with a pressure gauge. The apparatus is purged with nitrogen for 15 minutes. The airtightness is then checked as described in Example 1. Heating to the reaction temperature is carried out as described in Example 1. The temperature and pressure are maintained for 2.5 hours. At the end of this time, the apparatus is depressurized for 30 minutes and purged with nitrogen, and the temperature is maintained for another 3 hours under a nitrogen stream. The steel bomb tube is then removed from the metal bath and allowed to stand overnight at room temperature in a nitrogen stream.

[0113] Without the addition of a mediator, no conversion to a polymer could be detected by NMR or IR spectroscopy.

[0114] The salts serving as mediators are prepared by heating equimolar amounts of a diamine and a dicarboxylic acid in ethanol, distilling off a small amount of the solvent if necessary and removing water azeotropically.

[0115] Table 2: Reaction conditions and analytical results of Example 2, T = temperature, MAmt = amount of mediator in mol % based on the amount of pinene lactam used, Mono = monomer fraction (residual monomer content)

[0116]

[0117] PACM20: 4,4'-methylenebis(cyclohexylamine), with a trans-trans content of about 20%

[0118] DDA: 1,12-dodecanedioic acid

[0119] 12-ADA: 12-aminododecanoic acid, aminolauric acid

[0120] AH: Hexamethylenediamine + adipic acid

[0121] The product P2 was investigated by NMR spectroscopy in benzene solution.

[0122] Example 2, in which pinene lactam was used as a monomer, demonstrates the need to use a mediator.

[0123] It was also found that the best results were obtained using the mediator with the largest space requirement.

[0124] The glass transition temperature of polyamide is very high.

Claims

1. A method for preparing polyamide comprising the following steps: a) providing at least one bicyclic terpene lactam monomer, b) ring-opening polymerizing at least one bicyclic terpene lactam to provide a polyamide, wherein the phosphorus-containing acid is used in step b) in an amount of 2 to 100 ppm, based on the total mass of the monomers used, wherein a mediator is added in step b), It is characterized in that A mediator selected from nylon salts or α,ω-amino acids is used.

2. The method according to claim 1, wherein the polyamide is a homopolyamide or a copolyamide.

3. The method according to claim 1, characterized in that The amount of mediator used does not exceed 25% by weight of the amount of monomers used.

4. The method according to any one of claims 1 to 3, characterized in that The reaction temperature does not exceed 270°C.

5. A polyamide comprising at least 10% by weight of at least one cyclic terpenoid substructure, wherein: The substructure is derived from a monoterpene produced according to the process according to any one of claims 1 to 4, characterized in that the polyamide contains 1 to 100 ppm of phosphorus-containing components, Characterized in that the residual monomer content of the polyamide is 3 wt % to 20 wt % of the total mass of the polyamide.

6. The polyamide according to claim 5, characterized in that The polyamide has three-membered rings, four-membered rings and / or five-membered rings in its cyclic terpenoid substructure.

7. The polyamide according to any one of claims 5 to 6, characterized in that The cyclic terpenoid substructure includes a ring having two geminal methyl groups.

8. The polyamide according to any one of claims 5 to 6, characterized in that The polyamide has a four-membered ring in its cyclic terpenoid substructure and a molar mass of at least 3500 g / mol, or the polyamide has a three-membered ring in its cyclic terpenoid substructure and a molar mass of at least 8000 g / mol.

9. A molding composition comprising 10% to 90% of at least one polyamide according to any of claims 5 to 8 or a polyamide prepared by a process according to any of claims 1 to 4.

10. A shaped article produced from the molding composition according to claim 9.

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