EP3973012A1 - Polyamides à sous-structures terpénoïdes cycliques - Google Patents

Polyamides à sous-structures terpénoïdes cycliques

Info

Publication number
EP3973012A1
EP3973012A1 EP20726438.3A EP20726438A EP3973012A1 EP 3973012 A1 EP3973012 A1 EP 3973012A1 EP 20726438 A EP20726438 A EP 20726438A EP 3973012 A1 EP3973012 A1 EP 3973012A1
Authority
EP
European Patent Office
Prior art keywords
polyamides
substructure
weight
cyclic terpenoid
lactam
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20726438.3A
Other languages
German (de)
English (en)
Inventor
Frank Weinelt
Franz-Erich Baumann
Janina KOSSMANN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Operations GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Operations GmbH filed Critical Evonik Operations GmbH
Publication of EP3973012A1 publication Critical patent/EP3973012A1/fr
Pending legal-status Critical Current

Links

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
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
    • 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
    • C08G69/16—Preparatory processes
    • 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

Definitions

  • the present invention relates to polyamides containing cyclic terpenoid substructures.
  • Polyamides can be made from the condensation of diamines with dicarboxylic acids as well as amino acids or lactams. In the latter, the amino group and the carboxyl group are both functional groups required for linkage in the same molecule.
  • Lactams of camphor and menthone have been described in the literature (Kumar, Med. Chem. Res. 2012, p. 531). The lactams from ⁇ -pinene and 3-carene are also known from the literature (R. E. Gawley, Org. React. 1988, 35, 1). Lochinski et al. (Tetrahedron: Asymmetry, 2000, 1 1, 1295) discloses the lactam from 3-carene and the ring-opened one made from it
  • DE10 2014 221061A1 discloses the use of at least one terpene lactam for the production of polyamides.
  • the application discloses an example based on camphor lactam, which should be reacted with e-caprolactam to form a copolymer.
  • a certain amount of sodium lactamate (as a so-called catalyst) and a small amount of acyl caprolactam (as a so-called activator) are used here. Unreacted residual monomers were determined from the resulting polymer.
  • 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 using Benzoyl chloride and sodium lactamate are disclosed.
  • MALDI-TOF spectra show the formation of low molecular weight oligomers of menthone lactam.
  • Winnacker (Macromol. Rapid Commun., 2017 (40) 1800903) discloses acid-catalyzed
  • PA6 contains about 10% monomer in the product.
  • the monomer acts as a plasticizer and changes the mechanical properties of the product in such a way that it cannot be used in this form.
  • the residual monomer content can be reduced via a selection of further process steps.
  • EP3143069A1 discloses disadvantages such as low molar mass and low viscosity of polyamides caused by an excessively high content of residual monomers.
  • the present invention relates to a process for the production of polyamides with the addition of a small amount of phosphorus-containing acid and a mediator.
  • the present invention also relates to polyamides containing at least 10% by weight of at least one cyclic terpenoid substructure, the substructure preferably being derived from a monoterpene, which can be produced by the process according to the invention.
  • the present invention also relates to molding compositions containing 10 to 90% by weight of at least one polyamide according to the invention.
  • Another object of the invention is a shaped object produced from the molding composition according to the invention.
  • the shaped article is a molded part, a film, a bristle, a fiber or a foam.
  • the molded article can be produced, for example, by pressing, foaming, extrusion, coextrusion, blow molding, 3D blow molding, coextrusion blow molding, coextrusion 3D blow molding,
  • Coextrusion suction blow molding or injection molding Such methods are known to the person skilled in the art.
  • Another object of the invention is the use of the molded article according to the invention, which can be used, for example, as a fiber composite component, shoe sole, top coverings for skis or snowboards, media lines, glasses frames, design articles, sealing material, body protection, insulating material or foiled housing part.
  • Disclosure of the present invention include. If percentages are given below, then, unless otherwise stated, information is given in% by weight. In the case of compositions, the percentages relate to the total composition, unless otherwise stated. If mean values are given below, they are mass mean (weight mean) unless otherwise stated. If measured values are given below, these measured values were determined at a pressure of 101325 Pa and a temperature of 25 ° C, unless otherwise stated.
  • the possibly different units of the polyamide are randomly distributed.
  • Statistical distributions are built up in blocks with any number of blocks and any sequence or they are subject to a randomized distribution, they can also be built up alternately or also form a gradient across the polymer chain, in particular they can also form all mixed forms in which groups may be different distributions can follow one another. Special executions can result in the statistical distributions being restricted by execution. For all areas that are not affected by the restriction, the statistical distribution does not change.
  • One advantage of the polyamides according to the invention is that they are transparent.
  • polyamides according to the invention contain a considerable proportion by mass of renewable raw materials.
  • residual monomers denote the low molecular weight fraction with a molar mass of less than 500 g / mol.
  • the measurements were carried out by means of GPC as explained in the examples. Contents are% by weight.
  • Another advantage is the ability to adjust the properties of copolyamides based on bicyclic terpene lactams.
  • the products of the polymerization of pinene lactam have exceptionally high glass transition temperatures.
  • the cyclic terpenoid substructures can optionally contain a double bond.
  • the polyamides according to the invention preferably have three-membered, four-membered and / or five-membered rings in their cyclic terpenoid substructure.
  • the polyamides according to the invention more preferably have 10 carbon atoms in their cyclic terpenoid substructure.
  • the cyclic terpenoid substructure preferably contains a ring which preferably has two geminal methyl groups.
  • the ring is more preferably a 1, 1-dimethyl-cyclopropane,
  • 1,1-dimethyl-cyclobutane or 1,1-dimethyl-cyclopentane and optionally mixtures of these rings.
  • the 1,1-dimethyl-substituted rings have the substituents of the polymer-forming chain exclusively in the a and a'-positions, ie in both vicinal positions of the dimethyl-substituted ring member, at the end of which the functional groups for forming the amide groups are arranged.
  • the person skilled in the art is aware that in their position undefined groups must be arranged in such a way that two formal isoprenoid units are created through formal cutting of the claimed substructure.
  • the polyamides according to the invention preferably contain 1 to 100 ppm of a phosphorus-containing component; this component can be of inorganic or organic nature, preferably the inorganic component is an inorganic acid, more preferably hypophosphorous acid. More preferably, the polyamides contain 2 to 100 ppm, more preferably 5 to 60 ppm, the content data relating to the total mass of the polyamides.
  • the polyamides according to the invention preferably have a residual monomer content of 3 to 20% by weight, preferably 5 to 15% by weight, more preferably 7 to 13% by weight of the total mass of the polyamides.
  • the polyamides according to the invention preferably have a molar mass (number
  • the polyamide has a molar mass of at least 3500 g / mol and a proportion of at least 50% by weight consisting of a cyclic terpenoid substructure, the cycle having 4 ring members.
  • the polyamide more preferably has at least 60% by weight, in particular at least 70% by weight and at most 95% by weight, preferably at most 90% by weight, especially preferably at most 85% by weight of the cyclic terpenoid substructure with 4 ring members on.
  • the polyamides according to the invention preferably have a molar mass (number
  • the polyamide has a molar mass of at least 8000 g / mol and a proportion of at least 50% by weight consisting of a cyclic terpenoid substructure, the cycle having 3 ring members.
  • the polyamide more preferably has at least 60% by weight, in particular at least 70% by weight and at most 95% by weight, preferably at most 90% by weight, especially preferably at most 85% by weight of the cyclic terpenoid substructure with 3 ring members on.
  • the molar masses of the present invention are number-average molar masses (Mn) and can be determined according to the prior art; the molar masses are preferably determined by means of GPC or by determining the end groups, more preferably by means of GPC.
  • the polyamide according to the invention preferably contains at least one unit of a polyamide KL and / or M, the sum of the units from K + L + M being at least 2.
  • the unit K is derived from a diamine, L from of a diacid and M of an amino acid.
  • the polyamide according to the invention is thus a copolyamide.
  • the proportion of polyamide structures made from KL and / or M is preferably from 1 to 90% by weight, preferably from 2 to 75% by weight, more preferably from 3 to 60% by weight, more preferably from 5 to 50 Wt .-%, particularly preferably from 10 to 30 wt .-% and
  • the polyamides according to the invention preferably have a glass transition temperature greater than or equal to 100.degree. C., preferably 105.degree. C., more preferably 110.degree.
  • 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, particularly preferably less than or equal to 10% by weight.
  • the polyamide according to the invention preferably has, as a cyclic terpenoid substructure, at least 10 mol% of a cyclic terpenoid substructure with a four-membered ring, the content being based on the entire polyamide. Preferably this has
  • polyamide according to the invention at least 15 mol%, at least 20, 30, 40, 50, 60, 70, 80, 85, 90 and particularly preferably 95 mol% of the cyclic terpenoid substructure with a four-membered ring.
  • the polyamide according to the invention containing at least 10% by weight of at least one cyclic terpenoid substructure and the polyamide structures K.L and / or M, preferably has no further polyamides.
  • the polyamide according to the invention preferably has repeating units selected from the following cyclic terpenoid substructures:
  • the substructures 1 c ‘, 1 c”, 1’c ‘, 1’c”, 3c ‘, 3c”, 3’c ‘, 3’c”, 5c ‘and 5c“ are preferred.
  • the substructures 1 c ‘, 1 c ′′, 3c and 3c ′′ are particularly preferred.
  • the polyamides according to the invention can be produced according to the prior art, but preferably according to the method according to the invention, which comprises the following steps:
  • step b) Polymerizing the at least one bicyclic terpene lactam with ring opening, so that a polyamide, preferably a homopolyamide or a copolyamide, is obtained.
  • a phosphorus-containing acid is used in an amount of 2 to 100 ppm based on the total mass of the monomers used,
  • step a preference is given to bicyclic terpene lactams which, in addition to the lactam ring, have a three-ring, four-ring or five-ring.
  • Step b) is preferably carried out by adding a phosphorus-containing acid, more preferably hypophosphorous acid.
  • An amount from 2 to 100 ppm is preferably used, more preferably from 10 to 100 ppm, particularly preferably from 20 to 100 ppm, particularly preferably from 30 to 60 ppm.
  • the content data relate to the total mass of the monomers used.
  • Step b) is preferably carried out at “low” temperature, preferably below 270 ° C, more preferably below 260 ° C, 255 ° C, 250 ° C, 245 ° C and at least at 240 ° C.
  • the reaction time in step b) at a temperature of at least 240 ° C. is preferably kept “not too long”, preferably up to 10 hours, 8, 7, 6, 5, 4; with a minimum of 2 hours.
  • the pressure (“high pressure”) established at the reaction temperatures in step b) is preferably maintained over 10 to 90% of the reaction time, then the pressure relative to the environment is reduced and the remainder of the reaction time is at a pressure of 1 to 1.2 leave cash. More preferably, the high pressure is maintained at 20 to 80%, particularly preferably 30 to 70%, and particularly preferably 40 to 60%.
  • step b) preference is given to using a mediator which reacts into the polyamide according to the invention, 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.
  • Preferred mediators are nylon salts or a, w-amino acid (as
  • the mediator is preferably used in an amount of at most 25% by weight, 20% by weight, 15% by weight, 10% by weight, 5% by weight, particularly preferably 5 to 17% by weight, 8 up to 15% by weight, 9 to 13% by weight based on the amount of monomers used, particularly preferably based on the amounts of bicyclic terpene lactams used.
  • the nylon salt consists of an ⁇ , w-diammonium and an ⁇ , w-dicarboxylate compound; the nylon salt is preferably aliphatic.
  • the diammonium compound is preferably not linear; diammonium compounds with more than 6 up to 25 are more preferred
  • Diammonium compounds that have at least one ring structure are more preferred.
  • Diammonium compounds which have a PACM (4,4'-methylenebis [caclohexanamine]) structure are particularly preferred.
  • Dicarboxylate compounds with more than 6 up to 25 carbon atoms are preferred.
  • Particularly preferred are diammonium compounds with at least one ring structure and dicarboxylate Compounds with more than 6 up to 25 carbon atoms.
  • pene lactam is understood to mean a chemical compound which has at least one bicyclic system, one ring containing an amide bond -NH-CO-.
  • Isomers are known to the person skilled in the art; in particular, reference is made to the definitions of Prof. Kazmaier of Saarland University, e.g. B. http: //www.uni- saarland.de/fak8/kazmaier/PDF_files/vorlesungen/Stereochemie%20Strassb%20Vorlage.pdf referenced.
  • B. pinene basically all isomers are meant, the isomers occurring naturally in each case are preferred, in the case mentioned here so the a-pinene.
  • Terpene derivatives can be synthetic or partially synthetic in nature or as
  • Natural product isolated from a living being in the biosphere or another source The starting materials are preferably obtained from residues from cellulose production and then synthetically converted into the corresponding lactams.
  • tacticity e.g. B. isotactic, syndiotactic, heterotactic, hemiisotactic, atactic.
  • preference is given to polyamides with at least some atactic substituent sequences.
  • the bicyclic terpene lactams have several stereocenters.
  • particularly preferred bicyclic terpene lactams have a three-ring, four-ring or five-ring.
  • the bicyclic terpene lactams are preferably selected from corresponding bicyclic ones
  • the bicyclic terpene ketones are preferably made from corresponding bicyclic, simple unsaturated terpenes or corresponding bicyclic hydroxylated terpenes.
  • the ketones are particularly preferably produced from the following precursor molecules:
  • bicyclic terpene ketones are:
  • bicyclic three-ring terpene lactams are:
  • bicyclic four-ring terpene lactams are:
  • Particularly preferred bicyclic five-membered terpene lactams are: Particularly preferred bicyclic terpene lactams are those of the formulas 1 b ', 1 b ", 1'b', 1'b", 3b ', 3b ", 3'b', 3'b", 5b 'and 5b ".
  • no metal lactamates are used in the process according to the invention.
  • N-acyl-lactams are used in the process according to the invention.
  • step a) The polymerization of all lactams and bifunctional compounds provided in step a) preferably takes place in step b). More preferably there is a conversion of at least 95%, preferably at least 90%, particularly preferably at least 85%. The conversion is determined via the content of residual monomers in the polyamide according to the invention.
  • the present invention also provides a polyamide produced by the process according to the invention.
  • FIG. 1 describes the influence of temperature on the number-average molar mass (Mn) with a reaction time of 6 hours for a polyamide consisting of substructure units derived from carene.
  • the lactam consisted of at least 95 mol% of 3R, 4S, 6R-carene lactam.
  • Figure 2 describes the influence of temperature on the residual monomer content in a
  • the samples are dissolved in m-cresol at 30 ° C (0.005 g / ml) and measured at 25.00 ° C in a viscosity measuring system (LAUDA PVS or Schott AVS Pro).
  • Hexafluoroisopropanol dissolved with the addition of 0.05 mol / l potassium trifluoroacetate.
  • the measurements are driven with HFIP and 0.05 mol / l potassium trifluoroacetate at a flow rate of 0.8 ml / min with RI detection, calibration was carried out against 12 narrow distribution PMMA standards (M P between 505 g / mol and 4 ⁇ 10 6 g / mol).
  • the carboxyl end groups were determined alkalimetrically in benzyl alcohol and the amino end groups were determined in m-cresol at 100 ° C. using the 809 Titrando, Metrohm.
  • Double column system with two separating columns of different polarity. Unless otherwise specified, the samples are dissolved in toluene.
  • FID Flame ionization detector
  • PACM20 4,4 'methylenebis (cyclohexylamine) with 20% trans-trans content
  • DDS 1, 12-dodecanedioic acid
  • 12-ADS 12-aminododecanoic acid, aminolauric acid
  • Example 2 shows the need to use a mediator when pinene lactam is used as the monomer.
  • the glass transition temperature is unusually high for polyamides.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Polyamides (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des polyamides qui contiennent au moins 10 % en poids d'au moins une sous-structure terpénoïde cyclique. Cette sous-structure est de préférence dérivée d'un monoterpène. L'invention concerne en outre un procédé de production de ces polyamides, ainsi que des matières à mouler. Ces matières à mouler contiennent de 10 à 90 % en poids desdits polyamides.
EP20726438.3A 2019-05-20 2020-05-19 Polyamides à sous-structures terpénoïdes cycliques Pending EP3973012A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19175334.2A EP3741790A1 (fr) 2019-05-20 2019-05-20 Polyamide à sous-structures de terpénoïdes cycliques
PCT/EP2020/063949 WO2020234289A1 (fr) 2019-05-20 2020-05-19 Polyamides à sous-structures terpénoïdes cycliques

Publications (1)

Publication Number Publication Date
EP3973012A1 true EP3973012A1 (fr) 2022-03-30

Family

ID=66625061

Family Applications (2)

Application Number Title Priority Date Filing Date
EP19175334.2A Withdrawn EP3741790A1 (fr) 2019-05-20 2019-05-20 Polyamide à sous-structures de terpénoïdes cycliques
EP20726438.3A Pending EP3973012A1 (fr) 2019-05-20 2020-05-19 Polyamides à sous-structures terpénoïdes cycliques

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP19175334.2A Withdrawn EP3741790A1 (fr) 2019-05-20 2019-05-20 Polyamide à sous-structures de terpénoïdes cycliques

Country Status (7)

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US (1) US20220227932A1 (fr)
EP (2) EP3741790A1 (fr)
JP (1) JP2022533364A (fr)
KR (1) KR20220011142A (fr)
CN (1) CN114127157A (fr)
BR (1) BR112021023172A2 (fr)
WO (1) WO2020234289A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3922758A1 (fr) 2020-06-10 2021-12-15 Evonik Operations GmbH Procédé de fabrication électrochimique d'acides alcanicarboxyliques par oxydation avec ouverture de cycle au moyen d'une électrode en mousse ni(o)oh dopée

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2510777A (en) * 1946-12-30 1950-06-06 Du Pont Polyamide treated with a hypophosphorous acid compound
FI106117B (fi) * 1998-02-06 2000-11-30 Optatech Oy Menetelmä syklisten monomeerien valmistamiseksi
US7001979B2 (en) * 2002-06-14 2006-02-21 H.B. Fuller Licensing & Financing Inc. Polyamide and composition and article including same
US9101138B2 (en) * 2013-03-14 2015-08-11 The United States Of America, As Represented By The Secretary Of Agriculture Methods and compositions utilizing lactams derived from camphor, verbenone or cat thyme oil for repelling blood-sucking and biting insects, ticks and mites
US20170081472A1 (en) 2014-05-16 2017-03-23 Basf Se Production of polyamides by hydrolytic polymerization and subsequent treatment in a kneader
DE102014221061B4 (de) * 2014-10-16 2019-05-29 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Auf Terpenlactam basierende Polyamide
CN107129572B (zh) * 2017-05-10 2019-06-14 南京工业大学 一种生物基聚酰胺及其制备方法

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Publication number Publication date
WO2020234289A1 (fr) 2020-11-26
KR20220011142A (ko) 2022-01-27
EP3741790A1 (fr) 2020-11-25
US20220227932A1 (en) 2022-07-21
CN114127157A (zh) 2022-03-01
BR112021023172A2 (pt) 2022-01-04
JP2022533364A (ja) 2022-07-22

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