EP3526276A1 - Nouvelle voie de synthèse de copolyamides aliphatiques-aromatiques statistiques et les copolyamides aliphatiques-aromatiques statistiques obtenus - Google Patents
Nouvelle voie de synthèse de copolyamides aliphatiques-aromatiques statistiques et les copolyamides aliphatiques-aromatiques statistiques obtenusInfo
- Publication number
- EP3526276A1 EP3526276A1 EP17783515.4A EP17783515A EP3526276A1 EP 3526276 A1 EP3526276 A1 EP 3526276A1 EP 17783515 A EP17783515 A EP 17783515A EP 3526276 A1 EP3526276 A1 EP 3526276A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aliphatic
- aromatic
- formula
- iii
- alkyl
- 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
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
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/12—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids with both amino and carboxylic groups aromatically bound
-
- 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
- C08G69/18—Anionic polymerisation
-
- 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
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
Definitions
- the present invention relates to thermoplastic polyamides.
- Polyamides, especially nylon 6, are very widely used in various sectors because of their mechanical properties, for example as a matrix for thermoplastic composites in the automotive field.
- Polyamide 6 is generally synthesized by two distinct routes: either hydrolytic polymerization or anionic polymerization, both based on the opening of the ⁇ -caprolactam ring.
- the anionic polymerization has the advantage of being able to carry out the polymerization at a lower temperature and thus to limit the secondary reactions, and moreover, the very low initial viscovisity of the mixture makes it possible to associate numerous manufacturing processes such as the infusion under vacuum.
- the aromatic PA6s obtained have glass transition temperatures (Tg) of less than 70 ° C. for aromatics levels that are too high for the industrial applications envisaged. Indeed, an increase in the aromatic content increases the overall cost of the process because of the additional cost of the raw materials and the decrease in the copolymerization rate.
- the process according to the invention combines anionic ring-opening polymerization and chain polycondensation with a new aromatic monomer, thereby obtaining high Tg and aromatic contents compatible with the industrial cost criteria.
- the present invention relates to a process for preparing an aliphatic-aromatic copolyamide of formula (I):
- p is an integer from 5 to 1 1;
- n is the average number of aromatic units
- m is the average number by number of aliphatic units
- R is a C6-C12 aryl group or a linear or branched C1-C6 alkyl group
- X + is an alkali metal cation or a magnesium halide ion (MgHal + ) or a phosphazenium ion (such as alkyl phosphazenium, especially t BuP4H +)
- the process according to the invention makes it possible to increase the Tg of the polyamides obtained, for an industrially compatible proportion of aromatic units in the copolymer.
- Copolymers having less than 50 mol%, or even less than 25 mol% of aromatic units can thus be prepared, for Tg higher than 50 ° C.
- the method according to the invention therefore makes it possible to envisage accessing high Tg by increasing the aromatic content.
- the anionic PA6 indeed has a Tg equal to 52 ° C while the aromatic PA6 prepared by the process according to the invention has a Tg of up to 75 ° C or even 80 ° C, for an aromatic content of about 20 ° C. %.
- the aromatic PA6s obtained according to the process according to the invention have Tg values of the order of 75 ° C. or even 80 ° C. for aromatic contents of less than 25%.
- the process according to the invention can therefore be carried out using the same reagents as those usually used for the synthesis of aliphatic polyamide, to which an aromatic amine (III) or a salt thereof ( ⁇ ) is added as aromatic comonomer.
- a cross-reaction between the aromatic amine or its salt and the lactam-type monomer takes place according to a so-called "activated monomer" mechanism.
- Statistical copolymer or “statistical distribution”: the statistical sequence of aromatic units within aliphatic sequences. The statistical distribution is generally manifested by the existence of a single Tg for a given copolymer.
- Block Copolymer means a copolymer consisting of an aliphatic block and an aromatic block.
- Alkali metal cation Li + , Na + , K + salts.
- Tg The glass transition temperature of a polymer, i.e., the temperature at which the polymer changes from a solid glassy state to a rubbery state. She is typically measured by thermal analysis such as differential scanning calorimetry (DSC). It can thus be measured in particular by means of apparatus such as Perkin-Elmer Diamond DSC or TA instrument DSC Q100 LN2 by varying the temperature for example between -20 and 40 ° C, at a speed typically between 5 and 20 ° C.min "1 for example of the order of 10 ° C.min " 1 . p is preferably 5 or 1 1.
- the ratio n / (m + n) can be in particular between 10 and 40%.
- C1 -C6 alkyl means methyl, ethyl, propyl, butyl, pentyl and hexyl groups, and the iso- and tert-corresponding isomers.
- C 6 -C 12 aryl means aromatic groups comprising 6 carbon atoms, such as phenyl and naphthyl groups.
- Activator any activator generally used for the synthesis of polyamide by ring opening.
- activator suitable for the invention there may be mentioned in particular acyllactam type compounds, for example the lactam of formula (IV):
- R ' is a linear or branched C1-C6 alkyl group or a C6-C12 aryl group, optionally substituted by a carbamoylcaprolactam group, such as ⁇ , ⁇ '-hexamethylenebis (2-oxo-1-azepanylcarboxamide) or hexamethylene -1,6-dicarbamoylcaprolactam.
- a carbamoylcaprolactam group such as ⁇ , ⁇ '-hexamethylenebis (2-oxo-1-azepanylcarboxamide) or hexamethylene -1,6-dicarbamoylcaprolactam.
- activators commercially available activators range Bruggolen ® marketed by Bruggeman, including Bruggolen ® C20 P.
- the process according to the invention is carried out thanks to the active form of the amine (III), that is to say the alkyl 4-aminobenzoate salt of formula ( ⁇ ).
- this salt may be previously formed by deprotonation of the free form of the amine of formula (III) corresponding, by the action of a strong base.
- the salt ( ⁇ ) is formed in situ by the action of 4-aminobenzoate alkyl (III) with said strong base.
- salt (II ') with respect to the free form (III) be formed and engaged in the reaction.
- the process when the reaction is carried out from the alkyl 4-aminobenzoate ( ⁇ ) salt, the process may further comprise the prior step of pre-forming the salt from the 4-aminobenzoate of alkyl (III) and said strong base.
- the salt thus formed can be directly engaged in the reaction with the lactam derivative (II) and the activator, or can be isolated and / or purified intermediately before conducting said reaction.
- the step of deprotonation of the compound (III) by said strong base is preferably carried out in a polar, non-protic solvent.
- a solvent there may be mentioned tetrahydrofuran (THF), diethyl ether, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), acetonitrile.
- THF is generally preferred.
- the strong base can also be added in solid form (depending on the nature of the strong base used).
- the polymerization reaction can be carried out from the compound (II) in free form. It can further implement the salt of lactam (II).
- the salt of the lactam of formula (II) corresponds to formula ( ⁇ ):
- Y + represents an alkali metal cation, or a magnesium halide ion (MgHal + ) or a phosphazenium ion (such as alkyl phosphazenium, especially t BuP4H +, it being understood that Y + may be equal to X + .
- initiator is generally formed in situ in the presence of the compound (II) and the salt ( ⁇ ) and / or residues of the strong base present in the reaction mixture or present in the salt ( ⁇ ) when the latter is engaged as such This salt may also be added to the reaction mixture comprising said lactam (II) in order to promote the copolymerization reaction.
- omega-lauryllactam the salt ( ⁇ ) being designated omega-lauryllactamate.
- R is an ethyl group.
- the strong base is chosen from bases having a pKa greater than or equal to 25.
- bases having a pKa greater than or equal to 25 there may be mentioned as a suitable base for the process according to the invention: NaHMDS, LiHMDS, alkylmagnesiens, alkyllithiums, alkali metal hydrides, more particularly NaHMDS, LiHMDS.
- the polymerization reaction is conducted using 10 to 50 mol%, especially 10 to 40 mol%, of the compound ( ⁇ ) relative to the monomer (II).
- the base is generally used in a stoichiometric amount relative to the compound (III). This amount may however be lower, especially up to 10 mol% relative to the compound (III).
- the process according to the invention notably allows access to the aromatic aliphatic copolyamide of formulas
- the copolyamide PA6 / PA Ar according to the invention generally has a glass transition temperature Tg of between 50 ° C. and 75 ° C., or even 80 ° C. for an aromatic content of less than 20 mol%.
- the method according to the invention comprises the implementation of the bulk polymerization reaction, that is to say without polymerization solvent.
- reaction mixture when the reaction is conducted from the compound (III) in free form, without isolation step of the salt ( ⁇ ) formed intermediately, the reaction mixture can then contain the solvent of the deprotonation step.
- the present invention also relates to the random aliphatic-aromatic copolyamide of formula (I):
- p is an integer from 5 to 1 1;
- n is the average number of aromatic units
- m is the average number by number of aliphatic units
- / represents the statistical sequence of the aliphatic and aromatic units.
- p is preferably 5 or 1 1.
- m is between 0.5 and 0.95.
- n is between 0.05 and 0.5.
- the copolymers (I) have a dispersity of between 2 and 3.
- the number-average molar mass (Mn) is generally between 2,000 and
- HFIP hexafluoroisopropanol
- the measurements in HFIP can be performed with an integrated PL GPC50 system equipped with infra-red and UV (280 nm) and two columns PL HFIP gel
- the molar mass can be adapted according to the desired properties and the intended uses.
- the Tg of the aliphatic-aromatic copolyamides according to the invention can be between 50 ° C. and 90 ° C., in particular 50-80 ° C., particularly 50-75 ° C.
- the invention relates in particular to the random aliphatic-aromatic copolyamide of formula (I) corresponding to formula ( ⁇ ):
- PA6 / PA Ar according to the invention generally has a Tg between 50 ° C and 75 ° C, especially for an aromatic content of less than 20%.
- the present invention also relates to thermoplastic composites comprising, as polyamide, a copolymer according to the invention.
- the invention therefore also relates to automobile parts comprising said composite.
- ⁇ -Caprolactam (CL) (BASF, 99%) was recrystallized from dry cyclohexane prior to use.
- Bruggolen® C20 activator (17 wt% isocyanate in CL, N, N'-hexamethylenebis (2-oxo-1-azepanylcarboxamide) or hexamethylene-1,6-dicarbamoylcaprolactam in CL, Bruggemann Chemical) was used. as delivered.
- the 4-ethylaminobenzoate (98% Aldrich) was dried by azeotropic distillation with toluene (99.9% Aldrich) and was dried under vacuum for 12h.
- Tetrahydrofuran 99.9% THF, Aldrich
- Tetrahydrofuran 99.9% THF, Aldrich
- the toluene was dried over CaH 2 , refluxed overnight, distilled, then stored on polystyryl lithium.
- Sodium bis (trimethylsilyl) amide NaHMDS, 1.0 M in THF
- NaHMDS NaHMDS can also be used as a powder (95%, Aldrich) and then diluted in THF.
- the 4-ethylaminobenzoate (5.00 g, 29.55 mmol) is dried with 3 dry toluene azeotropes (3 * 20 ml)
- 3 dry toluene azeotropes (3 * 20 ml)
- argon (or nitrogen) 2.0 g (12.1 mmol) of 4-ethyl aminobenzoate then solubilized in THF (10 ml).
- the solution is cooled to 0 ° C before adding 12.5 ml of a solution of NaHMDS (1 M) in THF.
- the mixture is stirred at 25 ° C for 1 to 2 hours.
- the mixture is used as it is for the copolymerization.
- Polymerization Protocol In a reactor containing a magnetized bar and purged under argon (or nitrogen) at 140 ° C., 1 .mu.g (6.06 mmol) of activated monomer is introduced into 4 ml of dry THF. The mixture is maintained at 140 ° C. under a stream of argon (or nitrogen) until complete evaporation of the solvent, then ⁇ -caprolactam (CL, 6.16 g, 54.45 mmol) is added under an argon stream. The mixture is stirred for 5-10 minutes until complete fusion of ⁇ -caprolactam.
- Activator C20 (17% w / w isocyanate in CL, N, N'-hexamethylenebis (2-oxo-1-azepanylcarboxamide) or hexamethylene- 1,6-dicarbamoyl caprolactam in CL, Bruggemann Chemical) (415 mg, 0.180 mmol) is then added under an argon (or nitrogen) stream and the mixture is then held at 140 ° C for 40 min.
- the copolymers obtained in Example 1 were analyzed by DSC. Differential calorimetry (DSC) measurements of PA6 samples (approximately 10 mg) were performed on a TA instrument instrument DSC Q100 LN2 with a heating / cooling rate of 10 ° C / min for temperatures between -20 ° C and 250 ° C under nitrogen flow (10 mL / min) with aluminum crucibles. The results were collected from the second pass which led to Tg values evaluated from the point of inflection of the heat capacity jump.
- DSC Differential calorimetry
- Example 1 was reproduced by replacing 4-ethylaminobenzoate with ethyl 4-butylaminobenzoate as an aromatic monomer, according to the method described by Tune "Synthesis of Functionalized Polyamide 6 by anionic ring”. -opening polymerization ", March 2016. The following results were obtained: Example Tg (° C) content AHf (J / g) Tf (° C)
- the 4-ethylaminobenzoate (5.00 g, 29.55 mmol) is dried with 3 azeotropes with dry toluene (3 * 20 ml) and then used directly in powder form.
- Protocol deprotonation / polymerization Protocol deprotonation / polymerization
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1659918A FR3057569B1 (fr) | 2016-10-13 | 2016-10-13 | Nouvelle voie de synthese de copolyamides aliphatiques-aromatiques statistiques et les copolyamides aliphatiques-aromatiques statistiques obtenus. |
PCT/EP2017/076226 WO2018069515A1 (fr) | 2016-10-13 | 2017-10-13 | Nouvelle voie de synthèse de copolyamides aliphatiques-aromatiques statistiques et les copolyamides aliphatiques-aromatiques statistiques obtenus |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3526276A1 true EP3526276A1 (fr) | 2019-08-21 |
Family
ID=57539498
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17783515.4A Pending EP3526276A1 (fr) | 2016-10-13 | 2017-10-13 | Nouvelle voie de synthèse de copolyamides aliphatiques-aromatiques statistiques et les copolyamides aliphatiques-aromatiques statistiques obtenus |
Country Status (6)
Country | Link |
---|---|
US (1) | US10947344B2 (fr) |
EP (1) | EP3526276A1 (fr) |
JP (1) | JP7036812B2 (fr) |
CA (1) | CA3037646A1 (fr) |
FR (1) | FR3057569B1 (fr) |
WO (1) | WO2018069515A1 (fr) |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1083439B (it) * | 1976-08-26 | 1985-05-21 | Allied Chem | Composizioni di stampaggio a base di nailon caricato con sostanze minerali presentanti bassa deformazione permanente |
DE4119146C2 (de) * | 1991-06-11 | 2001-01-11 | Rehau Ag & Co | Polymer-Mischungen Verfahren zu ihrer Herstellung und ihre Verwendung |
CN106336508B (zh) * | 2016-09-14 | 2018-05-18 | 金发科技股份有限公司 | 一种半芳香族共聚酰胺树脂和由其组成的聚酰胺模塑组合物 |
-
2016
- 2016-10-13 FR FR1659918A patent/FR3057569B1/fr active Active
-
2017
- 2017-10-13 CA CA3037646A patent/CA3037646A1/fr active Pending
- 2017-10-13 JP JP2019520057A patent/JP7036812B2/ja active Active
- 2017-10-13 WO PCT/EP2017/076226 patent/WO2018069515A1/fr unknown
- 2017-10-13 US US16/335,049 patent/US10947344B2/en active Active
- 2017-10-13 EP EP17783515.4A patent/EP3526276A1/fr active Pending
Also Published As
Publication number | Publication date |
---|---|
JP7036812B2 (ja) | 2022-03-15 |
FR3057569A1 (fr) | 2018-04-20 |
WO2018069515A1 (fr) | 2018-04-19 |
US20190276604A1 (en) | 2019-09-12 |
CA3037646A1 (fr) | 2018-04-19 |
JP2019531392A (ja) | 2019-10-31 |
FR3057569B1 (fr) | 2018-11-30 |
US10947344B2 (en) | 2021-03-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0550314B1 (fr) | Polyamides et objets obtenus à partir de ceux-ci | |
EP2310438B1 (fr) | Polyamide semi-aromatique à terminaison de chaîne | |
EP0030903B1 (fr) | Compositions de polyamides polyphasées ayant des propriétés de résistance au choc améliorées et leurs procédés de préparation | |
EP2310439B1 (fr) | Copolyamide semi-aromatique et son procédé de préparation | |
EP1191050B1 (fr) | Procédé de polymérisation anionique de lactames | |
EP0030904B1 (fr) | Copolyesteramides souples à basse température | |
CA1161983A (fr) | Compositions polyphasees de polyamides et de polyesteramides | |
FR2724939A1 (fr) | Compositions thermoplastiques ignifugees a base de polyamide et leur application au revetement de cables electriques | |
WO2011045550A1 (fr) | Procede de preparation de poudre recyclable a base de polyamide | |
WO2010034803A2 (fr) | Composition polyamide renforcee | |
EP1165661B1 (fr) | Procede de polymerisation anionique de lactames | |
EP0553581B1 (fr) | Compositions amorphes transparentes à tenue aux agents chimiques élévée | |
EP3526276A1 (fr) | Nouvelle voie de synthèse de copolyamides aliphatiques-aromatiques statistiques et les copolyamides aliphatiques-aromatiques statistiques obtenus | |
WO2021160959A1 (fr) | Poudre de polyamide et procédé de préparation correspondant | |
FR2471399A1 (fr) | Compositions de polyamides polyphasees ayant des proprietes de resistance au choc ameliorees et leurs procedes de preparation | |
WO2008012480A2 (fr) | Procede de fabrication de poudre de polyamide a basse masse moleculaire et son utilisation | |
FR2692272A1 (fr) | Nouveaux polyamides cristallins à point de fusion élevé. | |
EP2958953B1 (fr) | Matériaux supramoléculaires à base d'oligo-amides | |
EP1311568A1 (fr) | Compatibilisant a base de polyolefine a greffons polyamide et melanges comprenant ce compatibilisant | |
FR2477562A1 (fr) | Compositions de polyamides polyphasees ayant des proprietes de resistance au choc ameliorees et leurs procedes de preparation. |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20190411 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20200423 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |