Classifications

• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
  • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
  • G01J3/28—Investigating the spectrum
  • G01J3/42—Absorption spectrometry; Double beam spectrometry; Flicker spectrometry; Reflection spectrometry
  • G01J3/433—Modulation spectrometry; Derivative spectrometry
  • G01J3/4338—Frequency modulated spectrometry
• • 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
• • 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
• • 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
  • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
  • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
  • G01J3/02—Details
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
  • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
  • G01J3/02—Details
  • G01J3/0297—Constructional arrangements for removing other types of optical noise or for performing calibration
• • G—PHYSICS
  • G02—OPTICS
  • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
  • G02C7/00—Optical parts
  • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
• • 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
  • C08L77/12—Polyester-amides
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/1397—Single layer [continuous layer]

Definitions

• Polyamide composition comprising such a polyamide and their uses.
• the present invention relates to a polyamide, to its method of preparation and to its uses, in particular in the manufacture of various objects, such as everyday consumer goods such as contact lenses, spectacle lenses, equipment electric, electronic or automotive, surgical equipment, packaging or sporting goods.
• the invention also relates to a composition comprising such a polyamide as well as to the uses of this composition, in particular in the manufacture of all or part of the objects which have just been enumerated above.
• transparent amorphous polyamides obtained by polycondensation of diamines and diacids are known.
• Such polyamides are particularly interesting because they have many mechanical properties such as impact resistance, tensile strength and / or compression, high resistance to external aggressions (such as heat, chemical agents, radiation).
• UV ultraviolet
• Transparent amorphous polyamides that are suitable for the manufacture of this type of object have in particular been described in documents EP 1 595 907 and US 2005/0272908 in the name of the Applicant. These polyamides are obtained by polycondensation of at least one cycloaliphatic diamine and at least 50 mol% of tetradecanedioic acid, the other diacid or dicarboxylic acid which may be chosen from aliphatic, aromatic and cycloaliphatic dicarboxylic acids. These polyamides have not only all of the properties mentioned above, but also a relatively high glass transition temperature Tg, typically of the order of about 130 ° C. to about 160 ° C.
• the object of the present invention is therefore to provide a polyamide having at least some of the mechanical properties mentioned above while having in their structure patterns from renewable raw material.
• the polyamides comprise at least two identical or distinct repeating units, these units being formed from the two corresponding monomers or comonomers.
• the polyamides are thus prepared from two or more monomers, or comonomers, chosen from an amino acid, a lactam and / or a dicarboxylic acid and a diamine.
• polyamide comprising at least one repeating unit corresponding to the following general formulation:
• X represents a cycloaliphatic diamine and Y represents an aliphatic dicarboxylic acid chosen from dodecanedioic acid (C 12), tetradecanedioic acid (C 14), hexadecanedioic acid (C 16), characterized in that said aliphatic dicarboxylic acid comprises organic carbon of renewable origin, also called bioressourcé determined according to ASTM D6866.
• the polyamide according to the invention may be a homopolyamide, when it comprises only identical X. Y units.
• the polyamide according to the invention may also be a copolyamide, when it comprises at least two distinct X. Y units.
• the copolyamides are denoted X.Y / Z, making it possible to distinguish the different comonomers.
• the polyamide according to the invention is a homopolyamide.
• a renewable raw material is a natural resource, animal or vegetable, whose stock can be reconstituted over a short period on a human scale. In particular, this stock must be renewed as quickly as it is consumed.
• polyamides are polymers whose durability is one of their essential qualities. Polyamides are generally used in applications for which the expected lifetimes are at least of the order of a decade.
• raw materials of renewable origin such as vegetable oil such as castor oil or palm oil for example
• polyamides of fossil origin do not capture during their lifetime, atmospheric CO2 (captured during photosynthesis for example). They release potentially at the end of life (example during incineration) a quantity of fossil CO2 of the order of 2.5 tonnes per tonne of polyamide, which had been previously collected in the fossil resource.
• fossil raw materials are used to make these polyamides, we contribute at the end of the life of the material, to reinject into the carbon cycle, the carbon that came out of it, since fossilized and on a time scale of the order millions of years old. In other words, this carbon comes extra in the cycle, causing an imbalance.
• the use of raw materials of renewable origin instead of raw materials of fossil origin contributes to reducing by at least 44% the quantities of
• renewable or biobased raw materials contain
• 14 C All carbon samples taken from living organisms (animals or plants) are in fact a mixture of 3 isotopes: 12 C (representing about 98.892%), 13 C (about 1, 108%) and 14 C (traces: 1, 2.10 10 %).
• the 14 C / 12 C ratio of living tissues is identical to that of the atmosphere.
• 14 C exists in two main forms: in mineral form, ie carbon dioxide (CO 2 ), and in organic form, that is to say of carbon integrated in organic molecules.
• CO 2 carbon dioxide
• the 14 C / 12 C ratio is kept constant by metabolism because carbon is continuously exchanged with the external environment.
• the proportion of 14 C being constant in the atmosphere, it is the same in the body, as long as it is alive, since it absorbs this 14 C in the same way as the 12 C ambient.
• the average ratio of 14 C / 12 C is equal to l, 2x l ⁇ ⁇ 12 . 12 C is stable, that is to say that the number of atoms of 12 C in a given sample is constant over time.
• - no is the number of 14 C at the origin (on the death of the creature, animal or plant),
• n is the number of 14 C atoms remaining at the end of time t
• - a_ is the disintegration constant (or radioactive constant); it is connected to the half-life.
• the half-life (or period) is the time after which any number of radioactive nuclei or unstable particles of a given species are halved by disintegration; the half-life T1 / 2 is related to the decay constant a_ by the formula In 2.
• the half-life of 14 C is 5730 years.
• the 14 C content is substantially constant from the extraction of renewable raw materials up to the manufacture of polyamides according to the invention and even up to the end of their use.
• the polyamides according to the invention comprise organic carbon (that is to say carbon incorporated in organic molecules) from renewable raw materials, which can be certified by determination of the 14 C content according to the invention. one of the methods described in ASTM D6866-06 Standard Test Methods for Determining the Biobased Content of Natural Range
• This standard ASTM D6866-06 includes three methods of measuring organic carbon from renewable raw materials, called in English biobased carbon.
• the proportions indicated for the polyamides of the invention are preferably measured according to the mass spectrometry method or the liquid scintillation spectrometry method described in this standard.
• polyamides which have mechanical, chemical and thermal properties of the order of those of the polyamides of the prior art obtained from diacids derived from of petrochemicals, this satisfying at least one of the sustainable development concerns mentioned above, namely limiting the use of fossil resources.
• the raw materials of plant origin have the advantage of being composed of compounds having essentially even numbers of carbon atoms, unlike monomers derived from petroleum fractions, which have, for their part, impurities comprising both odd and even carbon atom numbers.
• the impurities drained during the processes for converting products derived from raw materials of plant origin have essentially an even number of carbon atoms.
• the presence of these odd number of carbon atom impurities has a direct impact on the macromolecular structure of the final polyamide, leading to a disorganization effect of the structure. Therefore, some properties of the polyamide may be affected, such as crystallinity, melting temperature or glass transition temperature, for example.
• the monomer Y of the polyamide is obtained from diacids C 12, C 14 or C 16, themselves from renewable raw materials, which is identified from the ASTM D6866 standard.
• the content expressed as a percentage of renewable organic carbon in the polyamide according to the invention, denoted% C org . re nouv is strictly greater than 0, the content% C org. re nouv satisfying the equation (I):
• Fi, Fj, Fk respective molar fraction (s) of the monomers i, j and k in the polyamide
• the (co) monomers X and Y are monomers i, j and k within the meaning of equation (I).
• the polyamide contains a% C org content. re nouv greater than or equal to 20%, preferably greater than or equal to 40%, preferably greater than or equal to 50%, more preferably greater than or equal to 52%.
• polyamide according to the invention has a% C org renewal content of greater than or equal to 50%, it meets the criteria for obtaining the JBPA "Biomass PIa" certification, which is also based on the ASTM D6866 standard. Polyamide according to the invention can also validly bear the "Bio-mass-based" label of the JORA Association.
• the (co) monomer (s) may be derived from renewable resources, such as vegetable oils or natural polysaccharides such as starch or cellulose, the starch being extractable from, for example, maize or potato.
• This or these (co) monomers, or starting materials may in particular come from various conversion processes, including conventional chemical processes, but also enzymatic transformation processes or by bio-fermentation.
• the diacid C 12 (dodecanedioic acid) can be obtained by bio-fermentation of dodecanoic acid, also called lauric acid, lauric acid can be extracted from the rich oil of palm kernel and coconut, by example.
• the C 14 diacid (tetradecanedioic acid) can be obtained by bio-fermentation of myristic acid, the myristic acid can be extracted from the rich oil of kernal palm and coconut, for example.
• the diacid C 16 (hexadecanedioic acid) can be obtained by bio-fermentation of palmitic acid, the latter being found in palm oil mainly, for example.
• the monomer X of the polyamide according to the invention represents a cycloaliphatic diamine.
• cycloaliphatic diamines those comprising two rings are preferred. They respond in particular to the following general formula:
• R1 to R4 represent identical or different groups chosen from a hydrogen atom or alkyl groups of 1 to 6 carbon atoms and X represents either a single bond or a divalent group consisting of:
• a group of 8 to 12 carbon atoms consisting of a dialkyl, linear or branched, with a cyclohexyl or benzyl group.
• the cycloaliphatic diamine of the copolyamide according to the invention is chosen from bis (3,5-dialkyl-4-aminocyclohexyl) methane, bis (3,5-dialkyl-4-aminocyclohexyl) ethane, bis (3, 5-dialkyl-4-aminocyclohexyl) propane, bis (3,5-dialkyl-4-aminocyclohexyl) butane, bis (3-methyl-4-aminocyclohexyl) methane (BMACM or MACM), p-bis (aminocyclohexyl) methane (PACM) and isopropylidenedi (cyclohexylamine) (PACP).
• bis (3,5-dialkyl-4-aminocyclohexyl) methane bis (3,5-dialkyl-4-aminocyclohexyl) ethane
• the cycloaliphatic diamine is chosen from bis (3-methyl-4-aminocyclohexyl) methane (BMACM or MACM), in particular that marketed by BASF under the name Laromin® C260, and p-bis (aminocyclohexyl) -methane (PACM).
• BMACM bis (3-methyl-4-aminocyclohexyl) methane
• PAM p-bis (aminocyclohexyl) -methane
• PACM20 comprising of the order of 20% by weight of the trans / trans stereoisomer, in particular that marketed by the Air Products under the name Amicure® is more particularly preferred.
• cycloaliphatic diamines (BACM or PACM20) makes it possible, in most cases, to obtain a transparent polyamide, the transparency being characterized by a melting enthalpy of the polyamide having a value of between 0 and 12J / g.
• polyamides corresponding to one of the formulas chosen from MACM 12 will be selected; MACM.14, PACM.12, PACM.14.
• the nomenclature used to define polyamides is described in ISO 1874-1: 1992 "Plastics - Polyamides (PA) for molding and extrusion - Part 1: Designation", in particular on page 3 (Tables 1 and 2) and is well known to those skilled in the art.
• the molar proportions of cycloaliphatic diamine and of diacid are preferably stoichiometric.
• the polyamide is a copolyamide and may comprise at least two distinct units and have the following general formula: X.Y / Z
• X and Y are as defined above,
• Z being selected from a unit obtained from an amino acid, a unit obtained from a lactam and a unit having the formula (diamine Ca). (diacid in Cb), with a representing the number of carbons of the diamine and b representing the number of carbons of the diacid, a and b being each between 4 and 36.
• Z represents an amino acid
• it may be chosen from 9-aminononanoic acid, 10-aminodecanoic acid, 12-aminodecanoic acid and aminododecanoic acid and 11-aminoundecanoic acid and its derivatives, especially N-heptyl-11-aminoundecanoic acid.
• the copolyamides formed would then comprise three, four, ... or more, patterns, respectively.
• copolyamides are of particular interest: they are copolyamides corresponding to one of the formulas chosen from B 12/11, B.12 / 12, P 12/1 1, P .12 / 12, B.14 / 1 1, P.14 / 1 1, B.14 / 12, P.14 / 12, the number 1 1 symbolizing the monomer derived from 1 1 - aminoundecanoic acid, the number 12 after / symbolizing the pattern from laurolactam, P symbolizing the PACM diamine, B symbolizing the MACM diamine, the number 12 following the monomer B or P symbolizing dodecanedioic acid (C 12), the number 14 following the monomer B or P symbolizing tetradecanedioic acid (at C 14).
• the molar content of Z is between 2 and 80%, the molar content of cycloaliphatic diamine X being between 10 and 49% and the molar content of diacid Y being also between 10 and 49%. %.
• Z represents a lactam
• it may be chosen from pyrrolidinone, piperidinone, caprolactam, enantholactam, caprylolactam, pelargolactam, decanolactam, undecanolactam, and laurolactam.
• the Z motif is a unit corresponding to the formula (diamine Ca).
• (Cb diacid) the unit (Ca diamine) is of the formula H 2 N- (CH 2) a -NH 2, when the diamine is aliphatic and linear.
• the diamine When the diamine is cycloaliphatic, it is chosen from bis (3,5-dialkyl-4-aminocyclohexyl) methane, bis (3,5-dialkyl-4-aminocyclohexyl) ethane, bis (3,5-dialkyl) 4 aminocyclohexyl) propane, bis (3,5-dialkyl-4-aminocyclohexyl) butane, bis (3-methyl-4-aminocyclohexyl) methane (BMACM or MACM), p-bis (aminocyclohexyl) ) -methane (PACM) and isopropylidenedi (cyclohexylamine) (PACP).
• bis (3,5-dialkyl-4-aminocyclohexyl) methane bis (3,5-dialkyl-4-aminocyclohexyl) ethane
• the diamine is arylaromatic, it is chosen from 1,3-xylylenediamine and 1,4-xylylenediamine and their mixture.
• the fatty acid dimers mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of long-chain hydrocarbon-based unsaturated monobasic fatty acids (such as linoleic acid and oleic acid), as described in particular in the document EP 0 471 566.
• the diacid when it is cycloaliphatic, it may comprise the following carbon skeletons: norbornyl methane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di (methylcyclohexyl), di (methylcyclohexyl) propane.
• the diacid is aromatic, it is chosen from terephthalic acid, isophthalic acid and naphthalene diacid.
• terephthalic acid isophthalic acid and naphthalene diacid.
• comonomers or X. Y motifs occur and when Z is a (Ca diamine) unit.
• the copolyamide further comprises at least one third comonomer and corresponds to the following general formulation:
• A is selected from a unit obtained from an amino acid, a unit obtained from a lactam and a unit having the formula (Cd diamine). (diacid in Ce), with d representing the number of carbons of the diamine and e representing the number of carbons of the diacid, a and b being each between 4 and 36.
• the pattern A has the same meaning the Z pattern defined above.
• copolyamides XY / Z / A Among all the possible combinations for copolyamides XY / Z / A according to the last variant, particular mention will be made of copolyamides corresponding to one of the formulas chosen from B.12 / 1 1 /P.12, B.12 / 12 / P.12, B.14 / 1 1 / P.14, B .14 / 12 / P.14, B.12 / 1 1 / 6.10, B.12 / 12 / 6.10, P.12 / 1 1 / 6.10 , P.12 / 12 / 6.10,
• Z and A patterns can come from fossil resources or renewable resources, increasing the proportion of organic carbon in the final polyamide.
• the invention also relates to a method for preparing a polyamide as defined above comprising at least one polycondensation step of at least one diacid, comprising carbon of renewable origin or carbon bioressourcé on a cycloaliphatic diamine.
• the above preparation process can be completed by two steps preceding the previously mentioned polycondensation step: a) obtaining a fatty monoacid from a renewable raw material, such as, for example, vegetable or animal oils; optionally purification, b) preparation of a diacid from the fatty monoacid from the preceding step, for example by fermentation; said diacid is then polycondensed on a cycloaliphatic diamine.
• a renewable raw material such as, for example, vegetable or animal oils
• b) preparation of a diacid from the fatty monoacid from the preceding step for example by fermentation; said diacid is then polycondensed on a cycloaliphatic diamine.
• the invention also relates to a composition comprising at least one polyamide.
• a composition according to the invention may further comprise at least one second polymer.
• this second polymer may be chosen from a semi-crystalline polyamide, an amorphous polyamide, a semi-crystalline copolyamide, an amorphous copolyamide, a polyetheramide, a polyetheramide, a polyesteramide and their mixtures.
• this second polymer is obtained from a renewable raw material, that is to say, responding to the test of ASTM D6866.
• This second polymer may in particular be chosen from starch, which may be modified and / or formulated, cellulose or its derivatives such as cellulose acetate or cellulose ethers, poly lactic acid, glycolic polyacid and polyhydroxyalkanoate.
• composition according to the invention may also comprise at least one additive.
• This additive may especially be chosen from fillers, fibers, dyes, stabilizers, especially UV stabilizers, plasticizers, impact modifiers, surfactants, pigments, brighteners, antioxidants, natural waxes and their mixtures. .
• fillers there may be mentioned silica, carbon black, carbon nanotubes, expanded graphite, titanium oxide or glass beads.
• this additive will be of natural and renewable origin, that is to say responding to the test of ASTM D6866.
• amino acids, diamines, diacids are effectively linear, nothing forbids to consider that they can in all or part be branched, such as 2-methyl-1,5-diaminopentane, partially unsaturated.
• the C 18 dicarboxylic acid diacid may be octadecanedioic acid, which is saturated, or octadecenedioic acid, which, for its part, exhibits unsaturation.
• copolyamide according to the invention or the composition according to the invention can be used to form a structure.
• This structure may be monolayer when it is formed only copolyamide or the composition according to the invention.
• This structure may also be a multilayer structure, when it comprises at least two layers and that at least one of the various layers forming the structure is formed from the polyamide or the composition according to the invention.
• the structure may especially be in the form of fibers, a film, a tube, a hollow body, an injected part or a lens.
• the polyamide according to the invention or the composition according to the invention may advantageously be used for the manufacture of lenses, in particular optical lenses, spectacle lenses, eyeglass frames.
• the use of the polyamide or the composition according to the invention can also be envisaged for all or part of items of electrical and electronic equipment such as telephone, computer, multimedia systems.
• polyamides and compositions of the invention can be manufactured according to the usual methods described in the prior art. Reference is made in particular to DE 4318047 or US 6 143 862.
• the monomers used in tests A to H are as follows:
• AI 1 1-aminoundecanoic acid supplied by the company ARKEMA, CAS 2432-99-7,
• PACM20 p-bis (aminocyclohexyl) methane
• PACM20 21% by weight of trans / trans isomers, sold under the name Amicure® by the company AIR PRODUCTS, CAS 1761-71 -3, dodecanedioic acid (denoted DC 12 in Table 1) obtained from lauric acid,
• Example A The preparation method, transposable for all of Examples A to H, will now be described in detail for Example A. It is specified that the amounts by weight of additives indicated below are applicable for all Examples A to H.
• composition of Example A comprises the following monomers and additives (benzoic acid, hypophosphorous acid, Irganox® 1098, which is an antioxidant marketed by the company CIBA, demineralized water), in the following weight contents:
• hypophosphorous acid H3PO2
• This composition is introduced into a 92 l autoclave reactor which, once closed, is heated with stirring at 260 ° C. After a maintenance phase under autogenous pressure for 2 hours, the pressure is then decreased in 1.5 h to atmospheric pressure. The reactor is then degassed for approximately 1 h at 280 ° C. by a nitrogen sweep.
• the homopolyamide obtained is then extruded in the form of rods, cooled in a water tray at room temperature, and then granulated.
• the granules obtained are then dried at 80 ° C. for 12 hours under vacuum to reach a moisture content of less than 0.1%.
• the homopolyamides and copolyamides of Examples A to H are in accordance with the invention, in the sense that the content% Cor.sub.gr.sub.rev is strictly greater than 0.
• copolyamides of Examples A to H are in addition transparent.
• copolyamides comprising two or three distinct motifs have been explicitly described. However, there is no reason not to envisage copolyamides comprising more than three distinct units, for example four or five distinct units, each of these multiple units being obtained either from an amino acid or from a lactam, or with the formula (diamine). (diacid), provided that the polyamide contains organic carbon of renewable origin determined in accordance with ASTM D6866, ie the
• Lauric acid can be extracted from coconut oil or palm kernel oil.
• a dodecanedioic diacid can then be obtained by bio-fermentation, using the appropriate microorganism, from lauric acid.
• the diacid can then be aminated in the presence of ammonia and at least one strong base, without solvent.
• Myristic acid can be extracted from coconut oil or palm kernel oil.
• a tetradecanedioic diacid can then be obtained by bio-fermentation, using the appropriate microorganism, from myristic acid.
• the diacid can then be aminated in the presence of ammonia and at least one strong base, without solvent.
• Samples of each of the products obtained are analyzed semi-quantitatively by gas chromatography-coupled mass spectrometry.
• the internal standard used is the Tinuvin 770, and the column is of the type CP-SIL 5CB (Varian) with a length of 50m.
• This analysis makes it possible to identify a certain number of aliphatic diacid impurities, some containing an even number of carbon atoms and others odd, and to compare semi-quantitatively their reciprocal content.
• ⁇ amount of impurity containing an even number of carbon atoms
• the table below shows the quantities of atmospheric CO2 "out" of the carbon cycle, when a ton of the polyamides of the invention is produced.

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