WO2020070446A1 - Procede ameliore pour la fabrication de polyamides transparents - Google Patents
Procede ameliore pour la fabrication de polyamides transparentsInfo
- Publication number
- WO2020070446A1 WO2020070446A1 PCT/FR2019/052334 FR2019052334W WO2020070446A1 WO 2020070446 A1 WO2020070446 A1 WO 2020070446A1 FR 2019052334 W FR2019052334 W FR 2019052334W WO 2020070446 A1 WO2020070446 A1 WO 2020070446A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bis
- aminocyclohexyl
- methane
- methyl
- diamine
- Prior art date
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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
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
Definitions
- the present patent application relates to an improved process for the manufacture of transparent polyamides. It also relates to the use of a cycloaliphatic diamine having a specific isomeric composition to improve the transparency of polyamides and its stability after a heat treatment. The present application further relates to transparent polyamides capable of being obtained by such a process as well as articles made from such polyamides.
- Amorphous polyamides for example those described in application EP 0 313 436 A1, obtained from cycloaliphatic diamines and aromatic acids and from a lactam or amino acid, combine excellent transparency with high chemical resistance and their transparency resists by elsewhere with boiling water. These polymers are advantageous, for example, for the manufacture of sterilizable articles, such as respiratory masks, optical articles such as frames and glasses for glasses, as well as household electrical articles.
- the cycloaliphatic diamines most often used for the manufacture of transparent polyamides comprise two cyclohexane groups linked together by an alkylene group and each substituted by an amine group and, where appropriate, by one or more other alkyl substituents. Because of their chemical structure, these compounds exist in the form of numerous stereoisomers. Indeed, each substituent of cyclohexane can be in an equatorial or axial position on the cyclohexane and in a trans or cis position relative to the alkylene group connecting the two rings. Other possibilities for isomerism arise from the fact that the two cyclohexanes can take different conformations. As a result, these cycloaliphatic diamines generate a multitude of isomers.
- trans-trans isomers of PACM accelerate the crystallization of polyamides obtained by polycondensation with aliphatic diacids and, up to a content of 70%, increase the melting point and the glass transition (Prince, Frank R., Pearce, Eli M. "The effect of isomer ratio on the Properties of Bis (4-aminocyclohexyl) methane polyamides", Macromolecules 4/3, p.347-350, 5/1971).
- BMACM bis (3-methyl-4-aminocyclohexyl) methane
- BMACM diamine is marketed by various companies such as BASF, Sigma Aldrich and Jiangsu Qingquan Chemical Co., Ltd. These diamines are sold without specification of their stereoisomer composition, which can vary according to their production process, and over time following process changes.
- the object of the invention is to propose a manufacturing process for transparent polyamides based on cycloaliphatic diamines such as BMACM which is better controlled, and in particular which allows polyamides to be obtained, the transparency of which is retained following a heat treatment.
- the present invention is based on the discovery that it is possible, by selecting a particular isomeric profile of these diamines, to ensure satisfactory transparency of the polyamides, including when they have been exposed to heat.
- the idea underlying the present invention is to use a cycloaliphatic diamine with a specific isomeric profile in order to avoid the formation of these infusible structures and to obtain polyamides having a preserved transparency even when they are exposed to heat.
- the invention relates to a process for manufacturing transparent polyamides comprising a step of polycondensation of a mixture of monomers comprising at least one dicarboxylic acid and at least one cycloaliphatic diamine, in which said cycloaliphatic diamine comprises two rings linked by an alkylene group having 1 to 6 carbon atoms, each ring being substituted by an amine group and at least one alkyl group which may be identical or different, having 1 to 6 carbon atoms, characterized in that said cycloaliphatic diamine is broken down into six isomer fractions when subjected to gas chromatography analysis on a non-polar column and when said isomer fractions are called isomer fractions I to VI in their elution order, the mass content Fi in fraction of isomers I of said cycloaliphatic diamine does not exceed 35%.
- the cycloaliphatic diamine is further characterized by a mass content in fraction of Fn isomers which is greater than its mass content in fraction of F isomers
- the cycloaliphatic diamine is moreover characterized by a difference AF M / I between the mass content in fraction of isomers II and in fraction of isomers I which is greater than 0% and preferably greater than 5%.
- the process according to the invention is implemented with a cycloaliphatic diamine comprising two cyclohexane rings linked by a linear or branched alkylene group comprising 1 to 4 carbon atoms, in particular methylene or propylene, and in which the cyclohexane rings are each substituted by an amine group, preferably in position 4, and one or two linear or branched alkyl groups containing 1 to 6 carbon atoms, in particular methyl or ethyl.
- the diamine can be chosen from bis (3-methyl-4-aminocyclohexyl) methane (also called BMACM or MACM or B), 2,2 'bis (3-methyl-4-aminocyclohexyl) propane, bis (3-methyl-5-ethyl -4-aminocyclohexyl) methane, bis (3,5-dimethyl-4-aminocyclohexyl) methane, bis (3,5-dimethyl-4-aminocyclohexyl) propane, bis (2, 3-dimethyl-4-aminocyclohexyl) methane, bis (2,3-dimethyl-4-aminocyclohexyl) propane, bis (3,5-diethyl-4-aminocyclohexyl) methane, bis (3,5-diethyl-4 - aminocyclohexyl) propane, bis (3-methyl-5-isopropyl-4-aminocyclohexyl) methane and
- the process according to the invention is carried out with a dicarboxylic acid which is an aromatic dibasic acid, in particular terephthalic acid.
- the dicarboxylic acid can be a mixture of terephthalic acid and isophthalic acid comprising at least 50%, in particular at least 60% and very particularly at least 75 mol% of terephthalic acid.
- the polycondensation is carried out in the presence of one or more additional monomers.
- it can be carried out in the presence of one or more additional monomers forming a polyamide unit, such as a lactam, a w-amino acid or a salt of diamine and of dicarboxylic acid.
- the amino acid is preferably chosen from aminoundecanoic acid.
- the lactam is preferably chosen from lauryllactam.
- the process according to the invention is a process as defined above in which the cycloaliphatic diamine is bis (3-methyl-4-aminocyclohexyl) methane, the diacid is a mixture of acid terephthalic and isophthalic acid and polycondensation is carried out in the presence of aminoundecanoic acid.
- the process according to the invention is a process as defined above in which the cycloaliphatic diamine is bis (3-methyl-4- aminocyclohexyl) methane, the diacid is a mixture of terephthalic acid and isophthalic acid and the polycondensation is carried out in the presence of lauryllactam.
- the invention relates to the use of a cycloaliphatic diamine for the manufacture of a transparent polyamide, characterized in that the cycloaliphatic diamine is as described above.
- the diamine is chosen from bis (3-methyl-4-aminocyclohexyl) methane (also called BMACM or MACM or B), 2,2 'bis (3-methyl-4-aminocyclohexyl) propane, bis ( 3-methyl-5-ethyl -4- aminocyclohexyl) methane, bis (3,5-dimethyl-4-aminocyclohexyl) methane, bis (3,5-dimethyl-4-aminocyclohexyl) propane, bis (2,3 -dimethyl-4-aminocyclohexyl) methane, bis (2,3-dimethyl-4-aminocyclohexyl) propane, bis (3,5-diethyl-4-aminocyclohexyl) methane, bis (3,5-diethyl-4- aminocyclohexyl) propane, bis (3-methyl-5-isopropyl-4-aminocyclohexyl) methane and bis
- the invention relates to a transparent polyamide capable of being obtained by the method according to the invention.
- the invention relates to a formulation, in particular a transparent formulation obtained from such a transparent polyamide, by mixing with one or more other polymers, additives, fillers and / or modifiers.
- the invention relates to articles, in particular transparent articles obtained from such a transparent polyamide or from such a transparent formulation.
- Fig. 1 a gas chromatogram (GC) of a batch of BMACM (BMACM 1);
- Fig. 2 a gas chromatogram (GC) of another batch of BMACM (BMACM 2), and
- Fig. 3 a diagram illustrating the sources of stereoisomerism in diamine bis (3-methyl-4-aminocyclohexyl) methane.
- the term "monomer” must be taken in the context of polyamides in the sense of “repeating unit” or “repeating unit”. Indeed, the case where a repeating unit of the polyamide consists of the association of a diacid with a diamine is particular. It is considered to be the association of a diamine and a diacid, that is to say the diamine couple. diacid (in equimolar amount), which corresponds to the monomer. This is explained by the fact that individually, the diacid or the diamine is only one structural unit, which is not sufficient by itself to polymerize to give a polyamide.
- copolymer is intended to denote a polymer resulting from the copolymerization of at least two types of chemically different monomer, called comonomers.
- a copolymer is therefore formed from at least two repeating units. It can also be formed from three or more repeating patterns.
- amorphous polymer is intended to denote polymers having an enthalpy of fusion, as measured by differential calorimetry during the second heating with a heating rate of 20 ° C./min, at most equal to 30 J / g, in particular between 1 and 30 J / g or alternatively equal to 0 J / g.
- Haze value is understood to describe the transparency of a material in terms of light scattering at an angle greater than 2.5 ° from the normal observed following the interaction of light with inhomogeneities present in the material. . Unless otherwise stated, the Haze value was estimated by visual inspection of the presence or absence of a haze in the molten polymer in a test tube.
- isomers are understood to denote compounds having the same crude formula but a different developed or stereochemical formula.
- isomers of interest are in particular the stereoisomers, and among these the configuration isomers, that is to say the enantiomers and the diastereoisomers.
- the present invention relates to a process for the preparation of a transparent polyamide by polycondensation of a cycloaliphatic diamine with a dicarboxylic acid, and where appropriate other comonomers, in which the isomeric profile of the cycloaliphatic diamine is chosen so as to minimize the formation of infusible compounds.
- a process for the preparation of a transparent polyamide by polycondensation of a cycloaliphatic diamine with a dicarboxylic acid, and where appropriate other comonomers, in which the isomeric profile of the cycloaliphatic diamine is chosen so as to minimize the formation of infusible compounds.
- Such a process makes it possible to obtain a polyamide whose transparency, in terms of Haze, remains satisfactory even when the polyamide has been exposed to high temperatures, for example 300 ° C., for an extended period, for example for 24 hours, 48 hours or 72 hours.
- cycloaliphatic diamines exist in the form of numerous isomers, in particular stereoisomers.
- GC gas chromatography
- cycloaliphatic diamines used in the process according to the invention are broken down into six isomer fractions when they are subjected to gas chromatography (GC) on a nonpolar column, under the experimental conditions described in the examples below.
- GC gas chromatography
- BMACM which is a more complex cycloaliphatic diamine, since it carries an additional alkyl substituent on each cycle, is broken down into six isomer fractions.
- These isomer fractions are identified in the present description as "fractions I - VI", and numbered in their order of elution. Thus, the first eluted fraction is called the isomer I fraction, the second eluted fraction is called the isomer II fraction, etc.
- the mass content F x in fraction of isomer X is calculated from the areas of peaks Ai to A Vi of the fractions of isomers I to VI recorded on the diamine chromatogram as follows:
- the isomeric profile of a cycloaliphatic diamine is given by the relative proportion of each fraction of isomers, accessible by gas chromatography. It is therefore considered, taking into account their identical atomic composition and their very close chemical structure, that these proportions represent the mass content of each fraction of isomers in the cycloaliphatic diamine.
- the discovery at the basis of the invention is the observation that when such a cycloaliphatic diamine comprises 0 to 35%, preferably 0 and 33%, in particular between 0 and 30% of fraction of isomers I, the transparency of the polyamides in terms of Haze met expectations and was preserved even under the effect of heat.
- the cycloaliphatic diamine when the cycloaliphatic diamine is characterized by a mass content in fraction of Fn isomers which is greater than its mass content in fraction of Fi isomers, this was favorable in terms of Haze of the polyamide obtained.
- the cycloaliphatic diamine has an isomeric profile with a difference AFn / i between the mass content of fraction of isomers II and fraction of isomer I which is greater than 0% and preferably more than 5% and more particularly more than 10%.
- PACM is commercially available at different levels of trans-trans stereoisomers. It was thus possible to attribute among the three isomer fractions of this diamine the fraction of isomers leaving first in gas chromatography (GC) as being the trans-trans stereoisomers.
- GC gas chromatography
- the process according to the invention is implemented with a cycloaliphatic diamine comprising two cyclohexane rings linked by a linear or branched alkylene group comprising 1 to 4 carbon atoms, in particular methylene or propylene, and in which the cyclohexane rings are each substituted by an amine group, preferably in position 4, and one or two linear or branched alkyl groups containing 1 to 6 carbon atoms, in particular methyl or ethyl.
- the process according to the invention is implemented with a cycloaliphatic diamine comprising two cyclohexane rings linked by a linear or branched alkylene group comprising 1 to 4 carbon atoms, in particular methylene or propylene, and in which the cyclohexane rings are each substituted by an amine group, preferably in position 4, and one or two linear or branched alkyl groups containing 1 to 6 carbon atoms, in particular methyl or ethyl. It is preferred that the two rings of the cycloaliphatic diamine are linked to the same carbon atom of the alkylene group.
- a cycloaliphatic diamine chosen from bis (3-methyl-4-aminocyclohexyl) methane (also called BMACM or MACM or B), 2,2'bis (3-methyl-4-aminocyclohexyl) propane, bis ( 3-methyl-5-ethyl -4-aminocyclohexyl) methane, bis (3,5-dimethyl-4-aminocyclohexyl) methane, bis (3,5-dimethyl-4-aminocyclohexyl) propane, bis (2,3 -dimethyl-4-aminocyclohexyl) methane, bis (2,3-dimethyl-4-aminocyclohexyl) propane, bis (3,5-diethyl-4-aminocyclohexyl) methane, bis (3,5-diethyl-4- aminocyclohexyl) propane, bis (3-methyl-5-isopropyl-4-aminocyclohexyl) propane
- the process according to the invention is not particularly limited concerning the dicarboxylic acid (s) used.
- diacids can in particular be chosen from linear or branched aliphatic carboxylic acids containing 4 to 18 carbon atoms, in particular 4 to 12 and very particularly 4 to 6 carbon atoms.
- the dicarboxylic acid used comprises or consists of an aromatic diacid, in particular terephthalic acid.
- Terephthalic acid can be used alone or as a mixture with other dicarboxylic acids, in particular isophthalic acid.
- Particularly preferred is a mixture of terephthalic acid and isophthalic acid comprising at least 50%, in particular at least 60% and very particularly at least 75 mol% of terephthalic acid relative to the mixture of terephthalic and isophthalic acids.
- diamines having a specific isomeric profile has proven to be particularly useful in the manufacture of transparent polyamides comprising terephthalic acid, in particular more than 30% in particular more than 50%, in particular more than 60%, in particular more than 70%, in particular more than 80%, in particular more than 90%, very particularly 100% molar of terephthalic acid relative to the totality of moles of aromatic diacids in the mixture of monomers.
- terephthalic acid in particular more than 30% in particular more than 50%, in particular more than 60%, in particular more than 70%, in particular more than 80%, in particular more than 90%, very particularly 100% molar of terephthalic acid relative to the totality of moles of aromatic diacids in the mixture of monomers.
- polyamides based on terephthalic acid are particularly sensitive to transparency problems and that their sensitivity increases with the molar proportion of terephthalic acid in the mixture of dicarboxylic acids.
- the molar ratio between the diamine (s) and the diacid (s) is generally between 0.9: 1 to 1.1: 1, in particular between 0.95: 1 and 1.05: 1 and is therefore close to the stoichiometric ratio.
- the stoichiometric ratio is particularly preferred.
- Certain preferred transparent polyamides are obtained by polycondensation of a cycloaliphatic diamine with a diacid and in addition a lactam and / or a w-amino acid and / or a diamine and diacid salt.
- the lactam (s) preferably have at least 7 carbon atoms and preferably 9 to 12 carbon atoms. They can be chosen in particular from caprolactam, lauryllactam (or lactam 12) and undecanolactam. Lauryllactam is particularly preferred.
- the w-amino acid (s) preferably have at least 7 carbon atoms and preferably 9 to 12 carbon atoms.
- the w-amino acid (s) preferably have at least 7 carbon atoms and preferably 9 to 12 carbon atoms.
- 10-aminodecanoic acid there may be mentioned in particular 10-aminodecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
- Particularly preferred is 11-aminoundecanoic acid.
- the diamine in the diamine and dicarboxylic acid salt is preferably chosen from aliphatic or cycloaliphatic diamines containing 2 to 36, advantageously 4 to 18 and very particularly 6 to 16 carbon atoms.
- the dicarboxylic acid in the diamine and dicarboxylic salt is preferably an aliphatic or aromatic diacid advantageously comprising 4 to 36, advantageously 4 to 18 and very particularly 6 to 16 carbon atoms.
- the molar ratio between on the one hand the additional monomers and on the other hand the cycloaliphatic diamine (s) and the diacid (s) is generally between 0.3 / 1 and 2.8 / 1, preferably it is between 0.5 / 1 and 2.0 / 1 and even more preferred it is between 0.6 / 1 and 1.5 / 1.
- the process according to the invention is a process as defined above in which the cycloaliphatic diamine is bis (3-methyl-4-aminocyclohexyl) methane, the diacid is a mixture of acid terephthalic and isophthalic acid and polycondensation is carried out in the presence of aminoundecanoic acid.
- the process according to the invention is a process as defined above in which the cycloaliphatic diamine is bis (3-methyl-4-aminocyclohexyl) methane, the diacid is a mixture of terephthalic acid and isophthalic acid and polycondensation is carried out in the presence of lauryllactam.
- a diacid oligomer is prepared in a first step by condensation of all of the monomers, except the cycloaliphatic diamine.
- the reaction is generally carried out in a reactor under an inert atmosphere and / or under pressure while maintaining the reactants, preferably with stirring, at a temperature between 200 and 320 ° C. and preferably between 260 and 310 ° C.
- the reaction is generally carried out in 1 to 5 hours under atmospheric pressure or under autogenous pressure maximum of 30 bars.
- the cycloaliphatic diamine is added, under atmospheric pressure, to the diacid oligomer formed, which is reacted at a temperature between 200 and 350 ° C., and better still between 250 and 310 ° C.
- the reaction is generally carried out in an inert atmosphere in 1 to 6 hours under vacuum and / or atmospheric pressure and / or maximum pressure of 20 bars.
- the molar ratios used of diacid oligomer / cycloaliphatic diamine are between 1 / 0.9 and 1 / 1.1.
- catalysts of polyamidification such as phosphoric or hypophosphorous acid can be advantageously used. It is also possible in this second step to add to the reaction medium the additives such as light and / or heat stabilizers, dyes, optical brighteners, plasticizers, surfactants, nucleating agents, lubricants , mold release agents, flame retardants, chain regulators or defoamers.
- the additives such as light and / or heat stabilizers, dyes, optical brighteners, plasticizers, surfactants, nucleating agents, lubricants , mold release agents, flame retardants, chain regulators or defoamers.
- the monomers and any additives can be introduced into an autoclave reactor which is closed and then heated with stirring. After a phase of keeping under autogenous pressure for 2 hours, the pressure is then reduced in 1.5 hours to atmospheric pressure. The reactor is then degassed for approximately 1 hour. The copolyamide obtained is then extruded in the form of rods, cooled in a water tank at room temperature, then granulated.
- It can be a batch process or a continuous process.
- the polyamides thus obtained can then be formulated in order to optimize their properties.
- thermoplastic materials in particular other homo- or copolyamides, for example PAU, PA12, PA66, PA612, PA1010 and / or PA1012, in order to form alloys.
- These constituents are preferably added in an amount so as to represent 0 to 50% by weight of the alloy obtained.
- the mixing can for example be carried out by kneading in the molten state of granules, for example in an extruder.
- additives such as light and / or heat stabilizers, dyes, pigments, optical brighteners, plasticizers, surfactants, nucleating agents , lubricants, release agents, natural waxes, flame retardants, or chain regulators.
- fillers and modifiers to the polyamide, in particular in order to reinforce its mechanical performance.
- the formulation based on transparent polyamide can in particular be transparent.
- the charges and modifiers chosen are advantageously transparent. They can be chosen from beads or glass or carbon fibers or even impact modifiers.
- impact modifier should be understood to mean a polyolefin-based polymer having a flexural modulus of less than 100 MPa (as measured at 23 ° C according to ISO standard 178: 2010) and a Tg of less than 0 ° C (as measured according to standard 11357-2 at the point of inflection of the DSC thermogram), in particular a polyolefin, coupled or not with a Peba (polyether block amide) having a flexural modulus ⁇ 200 MPa. It would not go beyond the scope of the invention to use a Peba alone as a shock modifier in the composition.
- the polyolefin of the impact modifier can be functionalized or nonfunctionalized or be a mixture of at least one functionalized and / or at least one nonfunctionalized.
- some or all of the polyolefins carry a function chosen from the carboxylic acid, carboxylic anhydride and epoxide functions, and is in particular chosen from an ethylene-propylene copolymer of elastomeric character (EPR), an ethylene-propylene copolymer -diene with an elastomeric nature (EPDM) and an ethylene / (meth) alkyl acrylate copolymer, an ethylene-higher alkene copolymer, in particular an ethylene-octene copolymer, an ethylene-alkyl acrylate-maleic anhydride terpolymer.
- EPR ethylene-propylene copolymer of elastomeric character
- EPDM ethylene-propylene copolymer -diene with an elastomeric nature
- EPDM ethylene / (meth) alkyl acrylate copolymer
- an ethylene-higher alkene copolymer in particular an ethylene-
- the impact modifier is selected from Fusabond ® F493, a Pebax ®, particularly Pebax ® 40R53 SP01, a Lotader ®, especially Lotader ® 5500 or Lotader ® 7500, the Exxelor ® VA1803, or a mixture of these, in this case they are in a ratio ranging from 0.1 / 99.9 to 99.9 / 0.1, preferably 1/2 to 2/1 when they are a mixture of two.
- the impact modifier is chosen from the following mixtures: Fusabond ® 493 / Lotader ® , in particular Fusabond ® 493 / Lotader ® 5500 or Fusabond ® 493 / Lotader ® 7500.
- the impact modifier can also be a “core-shell” type modifier, also known as a “core-shell type copolymer”.
- the modifier of “core-shell” type is in the form of fine particles having an elastomer core and at least one thermoplastic shell, the particle size is generally less than ⁇ m and advantageously between 150 and 500 nm.
- the “core-shell” modifier has an acrylic or butadiene base, unlike the impact modifier, which has a polyolefin base.
- the proportion of impact modifier is between 0 and 10% by weight relative to the total weight of the composition.
- the transparent polyamides capable of being obtained by the process described, optionally in formulated form, are useful for the manufacture of articles, in particular transparent articles, of superior quality.
- BMACM reference standard Bis (3-methyl-4-aminocyclohexyl) methane mixture of stereoisomers - purity 99% (CAS 6864-37-5, marketed by Sigma-Aldrich)
- BMACM to analyze: BMACM 1 and BMACM 2
- Benzophenone (CAS 119-61-9, marketed by Sigma-Aldrich), in solution formed by the introduction of 250 mg into a volumetric flask of lOOmL supplemented with ethanol.
- GC Gas chromatography
- the samples were injected using an automatic sampler.
- the isomers are eluted in separate groups according to the volatilization temperature and the interaction with the column.
- the peak due to the internal standard there are six other peaks corresponding to the six BMACM fractions called isomer fractions I to VI in the order of exit from the chromatographic column.
- the impact of the isomeric profile of BMACM on the transparency of the polyamide was evaluated by preparing a polyamide with BMACM diamines of different isomeric profile and by estimating the Haze of the polyamide obtained after thermal exposure.
- Polyamide 12 / BI / BT was prepared as follows. In a suitable reactor fitted with a Paravisc-type stirrer, the raw materials are loaded in the proportions indicated in Table 5 below. Then, the reactor is inerted by 3 purges under 30 bar of nitrogen each followed by a return to atmospheric pressure. The reactor is then heated over 2 h 30 min to a temperature of 285 ° C. while stirring at 100 RPM. The reaction is maintained under the conditions of pressure and temperature for 2 h then the pressure is relaxed to atmospheric pressure in 1 h while aiming at a temperature of 290 ° C.
- BMACM As BMACM, BMACM 1, BMACM 2 and various mixtures of these two batches were used. The isomeric profile of the different batches and mixtures is indicated in Table 6 below.
- Table 5 Composition of the raw materials used for the synthesis of PA 12 / BI / BT
- the polyamides thus obtained initially exhibit zero Haze. They were then heated to 300 ° C in a test tube for 48 h under an inert atmosphere, during which time the Haze of the molten medium was evaluated visually at 300 ° C at different time intervals.
- the various polyamides 11 / BI / BT thus produced initially exhibit zero Haze. They were then heated to 300 ° C and maintained at this temperature under nitrogen sweep for 72 h. After cooling to room temperature, the Haze of the polyamides was evaluated visually. Table 9 below collates the results obtained. It can be seen that the Haze is zero for polyamides when the mixture of terephthalic acid and isophthalic acid comprises at most 50 mol% of terephthalic acid relative to the mixture of terephthalic and isophthalic acids (examples 2 and 3). When the mixture contains more terephthalic acid (Examples 4 and 5), the polyamide nevertheless still has a zero Haze when it was prepared with a BMACM having a mass content of fraction of isomers I not exceeding 35%.
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Abstract
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JP2021518627A JP2022504278A (ja) | 2018-10-03 | 2019-10-02 | 透明ポリアミドの製造方法の改良 |
EP19802241.0A EP3861053A1 (fr) | 2018-10-03 | 2019-10-02 | Procede ameliore pour la fabrication de polyamides transparents |
US17/282,067 US20220267519A1 (en) | 2018-10-03 | 2019-10-02 | Improved method for the production of transparent polyamides |
CN201980074852.6A CN113015759B (zh) | 2018-10-03 | 2019-10-02 | 用于生产透明聚酰胺的改进方法 |
KR1020217012820A KR20210068505A (ko) | 2018-10-03 | 2019-10-02 | 투명 폴리아미드의 개선된 제조 방법 |
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CN116063686A (zh) * | 2023-01-04 | 2023-05-05 | 万华化学集团股份有限公司 | 一种耐醇擦透明尼龙及其制备方法 |
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FR1541384A (fr) | 1966-10-18 | 1968-10-04 | Basf Ag | Procédé de fabrication de polyamides transparents |
EP0313436A1 (fr) | 1987-10-21 | 1989-04-26 | Elf Atochem S.A. | Polyamides transparents, leur procédé de fabrication |
WO2009153534A1 (fr) | 2008-06-20 | 2009-12-23 | Arkema France | Copolyamide, composition comprenant un tel copolyamide et leurs utilisations |
US20100022742A1 (en) * | 2006-01-31 | 2010-01-28 | Friedrich Severin Buhler | Polyamide molding compound and its use for producing transparent, hot-steam-sterilizable molded parts and extrudates |
US20110023986A1 (en) * | 2009-07-31 | 2011-02-03 | Ems-Patent Ag | Polyamide blend molding compound |
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DE2732928A1 (de) * | 1977-07-21 | 1979-02-01 | Bayer Ag | Transparente polyamide |
CH667462A5 (de) * | 1985-01-07 | 1988-10-14 | Inventa Ag | Transparente copolyamide, verfahren zu deren herstellung und deren verwendung zur herstellung von formkoerpern. |
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2018
- 2018-10-03 FR FR1859173A patent/FR3086946B1/fr active Active
-
2019
- 2019-10-02 EP EP19802241.0A patent/EP3861053A1/fr active Pending
- 2019-10-02 JP JP2021518627A patent/JP2022504278A/ja active Pending
- 2019-10-02 US US17/282,067 patent/US20220267519A1/en active Pending
- 2019-10-02 WO PCT/FR2019/052334 patent/WO2020070446A1/fr unknown
- 2019-10-02 CN CN201980074852.6A patent/CN113015759B/zh active Active
- 2019-10-02 KR KR1020217012820A patent/KR20210068505A/ko unknown
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Publication number | Priority date | Publication date | Assignee | Title |
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FR1541384A (fr) | 1966-10-18 | 1968-10-04 | Basf Ag | Procédé de fabrication de polyamides transparents |
EP0313436A1 (fr) | 1987-10-21 | 1989-04-26 | Elf Atochem S.A. | Polyamides transparents, leur procédé de fabrication |
EP0313436B1 (fr) | 1987-10-21 | 1993-07-28 | Elf Atochem S.A. | Polyamides transparents, leur procédé de fabrication |
US20100022742A1 (en) * | 2006-01-31 | 2010-01-28 | Friedrich Severin Buhler | Polyamide molding compound and its use for producing transparent, hot-steam-sterilizable molded parts and extrudates |
WO2009153534A1 (fr) | 2008-06-20 | 2009-12-23 | Arkema France | Copolyamide, composition comprenant un tel copolyamide et leurs utilisations |
US20110023986A1 (en) * | 2009-07-31 | 2011-02-03 | Ems-Patent Ag | Polyamide blend molding compound |
Non-Patent Citations (2)
Title |
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PRINCE, FRANK R.PEARCE, ELI M., MACROMOLECULES, vol. 4/3, May 1971 (1971-05-01), pages 347 - 350 |
PRINCE, FRANK R.PEARCE, ELI M.: "The effect of isomer ratio on the Properties of Bis(4-aminocyclohexyl)méthane polyamides", MACROMOLECULES, vol. 4/3, May 1971 (1971-05-01), pages 347 - 350, XP055602289, DOI: 10.1021/ma60021a020 |
Also Published As
Publication number | Publication date |
---|---|
US20220267519A1 (en) | 2022-08-25 |
CN113015759A (zh) | 2021-06-22 |
FR3086946B1 (fr) | 2021-06-25 |
FR3086946A1 (fr) | 2020-04-10 |
EP3861053A1 (fr) | 2021-08-11 |
CN113015759B (zh) | 2024-04-19 |
KR20210068505A (ko) | 2021-06-09 |
JP2022504278A (ja) | 2022-01-13 |
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