EP4136135A2 - Adhésif thermofusible résistant aux fluides automobiles - Google Patents

Adhésif thermofusible résistant aux fluides automobiles

Info

Publication number
EP4136135A2
EP4136135A2 EP21732383.1A EP21732383A EP4136135A2 EP 4136135 A2 EP4136135 A2 EP 4136135A2 EP 21732383 A EP21732383 A EP 21732383A EP 4136135 A2 EP4136135 A2 EP 4136135A2
Authority
EP
European Patent Office
Prior art keywords
copolyamide
unit
diamine
diacid
acid
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
EP21732383.1A
Other languages
German (de)
English (en)
French (fr)
Inventor
Quentin Pineau
Thomas PRENVEILLE
Pierre-Jean ROUMANET
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.)
Arkema France SA
Original Assignee
Arkema France SA
Bostik SA
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 Arkema France SA, Bostik SA filed Critical Arkema France SA
Publication of EP4136135A2 publication Critical patent/EP4136135A2/fr
Pending legal-status Critical Current

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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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/34—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty 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
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C09J177/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to copolyamides for the encapsulation of electronic devices, a process for preparing such a copolyamide, a composition containing it and its use.
  • this adhesive has the function of protecting the device from the environment, in which it is placed. It can come in contact with brake fluid, engine oil, gasoline, diesel, kerosene, alcohol, battery fluid or even coolant.
  • brake fluid engine oil, gasoline, diesel, kerosene, alcohol, battery fluid or even coolant.
  • These fluids are known to be very aggressive, especially when brought to high temperatures, especially during engine operation.
  • Today's car engines find themselves in an increasingly confined environment. The temperature of the air surrounding the engine is rising for reasons of efficiency and noise. The higher temperature will tend to increase the temperature of the liquids, making the latter even more aggressive towards the materials in contact with them.
  • These liquids, under the effect of higher temperatures, are particularly sensitive to oxidation, hydrolysis and degradation. This typically results in the formation of peroxides, which decompose into free radicals, which themselves attack the polymeric material of the automotive part in contact with said liquid. The resistance to aging in the face of these liquids must therefore be improved.
  • the invention relates to a semi-crystalline hot-melt copolyamide comprising at least two units corresponding to the following formula (1):
  • the X unit is a crystalline unit obtained by the polycondensation of a unit chosen from a C5 to C12 alpha, omega-aminocarboxylic acid, a C6 to C12 lactam and a unit (Ca diamine). (diacid in Cb), with a representing the number of carbon atoms of the diamine and b representing the carbon number of the diacid, a and b being greater than or equal to 4,
  • the Y unit is a unit obtained by the polycondensation of one unit (Cd diamine).
  • Cd diamine (Ce diacid), with d representing the number of carbon atoms of the diamine and e representing the carbon number of the diacid, d and e being between 24 and 48, the Cd diamine and the diacid in Ce being linear or branched aliphatic, saturated or unsaturated,
  • copolyamide comprising from 30 to 99.5% by mole of unit X and from 0.5 to 70% by mole of unit Y,
  • the invention also relates to a process for preparing the copolyamide according to the invention.
  • a subject of the invention is also a composition comprising the copolyamide according to the invention.
  • the invention relates to the use of this copolyamide or of the composition containing it to encapsulate electronic devices.
  • hot melt means the ability of the copolyamide to melt under the effect of heat.
  • polystyrene-crystalline copolyamide covers copolyamides which have both a glass transition temperature Tg and a melting temperature Tm.
  • Tg and Tf can be determined according to ISO 11357-2: 2013 and 11357-3: 2013 respectively.
  • polyamides The nomenclature used to define the polyamides is described in the ISO 1874-1: 1992 standard "Plastics - Polyamide materials (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.
  • PA denotes polyamide
  • L denotes the number of carbon atoms of the amino acid or else of the lactam.
  • the polyamide is obtained by the polycondensation of the amino acid or of the lactam comprising L carbon atoms.
  • M denotes the number of carbon atoms of the diamine and N denotes the number of carbon atoms of the diacid.
  • the semi-crystalline hot-melt copolyamide comprising at least two units corresponding to the following formula (1): X / Y (1).
  • the X unit is a crystal unit obtained by the polycondensation of a unit chosen from a C5 to C12 alpha, omega-aminocarboxylic acid, a C6 to C12 lactam and a unit (Ca diamine).
  • Cb diacid a representing the number of carbon atoms of the diamine and b representing the carbon number of the diacid, a and b being greater than or equal to 4, preferably a and b being between 5 and 48 .
  • the X unit can result from the polycondensation of one or more C5 to C12 alpha, omega-aminocarboxylic acids.
  • the alpha, omega-aminocarboxylic acid is selected from among 7-amino-heptanoic acid, 11-amino-undecanoic acid and 12-amino-dodecanoic acid.
  • the X unit can result from the polycondensation of one or more C6 to C12 lactams.
  • the lactam is chosen from caprolactam, enantholactam and lauryllactam.
  • the X unit can result from the polycondensation of a unit (diamine in Ca). (Cb diacid), with a representing the number of carbon atoms of the diamine and b representing the carbon number of the diacid, a and b being greater than or equal to 4.
  • a and b are between 5 and 48, more particularly, a is between 5 and 36 and b is between 8 and 48.
  • a is between 7 and 36, more particularly between 8 and 36, and very preferably between 9 and 36 and b is between 8 and 48.
  • the Ca diamine can be chosen from aliphatic, linear or branched diamines, cycloaliphatic diamines and alkylaromatic diamines.
  • the Ca diamine is aliphatic and linear, of formula H2N- (CH2) a-NH2
  • the Ca diamine can also come from the amination of polymerized fatty acids, as defined below.
  • the Ca diamine can be a C36 diamine.
  • the Ca diamine When the Ca diamine is aliphatic and branched, it may contain one or more methyl or ethyl substituents on the main chain.
  • it can advantageously be chosen from 2,2,4-trimethyl-1, 6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2-methyl-1, 5-pentanediamine, 2-methyl-1, 8-octanediamine.
  • the Ca diamine is alkylaromatic, it can be chosen from 1, 3-xylylenediamine and 1, 4-xylylenediamine.
  • the Ca diamine is piperazine.
  • the Cb diacid can be chosen from aliphatic, linear or branched diacids, cycloaliphatic diacids, aromatic diacids. Throughout the description, the expressions “diacid” or “dicarboxylic acid” or “dicarboxylic acid” denote the same product.
  • the diacid when it is cycloaliphatic, it may contain the following carbon skeletons: norbornyl, cyclohexyl, dicyclohexyl, dicyclohexylpropane.
  • the diacid is aromatic, it is chosen from terephthalic acid (denoted T), isophthalic (denoted I) and naphthalenic diacids.
  • the unit X is chosen from caprolactam, oenantholactam and lauryllactam, 7-amino-heptanoic acid, 11-amino-undecanoic acid and 12-amino-dodecanoic acid, PA510, PA610, PA 512, PA612, PA 514, PA614, PA618, PA pip10, PA pip36, PA1010, PA1012, PA1014, PA1018, PA1210, PA1212, PA1214 , PA1218. More particularly, the unit X is chosen from caprolactam, lauryllactam, amino-11-undecanoic, PA510, PA 512, PA610, PA 612, PA 1010, PA 1012 and PA pip36.
  • the unit X is chosen from an amino acid and a lactam, more particularly, the unit X is chosen from amino acids and the lactams have a number of carbon atoms greater than 6. More particularly, the unit X is PA6, PA11 or PA12.
  • the Y pattern is obtained by the polycondensation of a unit
  • the Cd diamine comes from the amination of polymerized fatty acids, as defined below. These diamines are commercially available under the trade name "Versamine” sold by the company Cognis Corporation (BASF) and under the trade name Priamine ® from Croda.
  • Ce diacid comes from polymerized fatty acids. These polymerized fatty acids denote the compounds produced from coupling reactions of unsaturated fatty acids, which lead to mixtures of products bearing two acid functions (called acid dimers) or three acid functions (called acid trimers). This coupling can be a reaction of combination or condensation of 2 moles of an unsaturated monocarboxylic acid, the mono acids can be the same or different. This dimerization reaction can be carried out according to catalytic or non-catalytic polymerization methods according to known methods.
  • the dimeric C36 diacid can be obtained by dimerization of a C18 unsaturated monoacid, such as oleic acid, linoleic acid, linolenic acid and their mixture. These mixtures are present for example in tall oil. In general, these mixtures mainly contain the dimer, and in lesser amounts the monomer, the trimer and oligomers. After separation, the fatty acid dimers are obtained predominantly from 75% to more than 98%, as a mixture with in particular the monomer, the 1 1/2 mer and the corresponding trimer.
  • a C18 unsaturated monoacid such as oleic acid, linoleic acid, linolenic acid and their mixture.
  • these mixtures are present for example in tall oil. In general, these mixtures mainly contain the dimer, and in lesser amounts the monomer, the trimer and oligomers. After separation, the fatty acid dimers are obtained predominantly from 75% to more than 98%, as a mixture with in particular the monomer, the
  • the final copolyamide may contain in its structure, in a very small amount, polycondensation products of the X unit, of the Cd diamine and of the monomers or trimers of the diacid in Ce present in the product. mixture of the dimer.
  • Di-dimeric acids can be obtained from C14 myristoleic acid, C16 palmitoleic acid, C16 sapienic acid, C18 oleic acid, C18 elaidic acid, trans acid - vaccenic C18, linoleic acid C18, linolelaidic acid C18, alpha-linolenic acid C18, gamma-linolenic acid C18, 11-eicosenoic acid 20, eicosapentaenoic acid in 20, dihomo-gamma-linolenic acid in C20, arachidonic acid in 20, erucic acid in 22, clupanodonic acid in C22, docosahexaenoic acid in C22, nervonic acid in 24 and their mixed.
  • Polymerized fatty acids are marketed and in particular the product of the trade name Pripol ® marketed by the company Croda can be used as well as the product of the trade name Empol ® marketed by the company Cognis or the product of the trade name Unydime ® marketed by Kraton or the trade name product Radiacid ® marketed by the company Oleon.
  • the fatty acid dimers can then be transformed into amine dimers, by transformation of the two acid functions into an amine function, or into amino acid dimers, by transformation of one of the acid functions into an amine function.
  • the diacids used for the Y unit are acidic dimers, and more particularly the C36 and C44 dimers are used.
  • the Y unit is chosen from PA 3636, PA 3644, PA 4436 and PA 4444.
  • the copolyamide according to the invention is PA 6/3636, PA 11/3636, PA 12/3636.
  • the copolyamide according to the invention does not contain ethylene diamine. Indeed, the inventors have observed that the presence of ethylenediamine deteriorates the chemical resistance properties of the material. It seems that this diamine participates in the swelling of the material in aggressive hot liquids.
  • the copolyamide according to the invention comprises from 30 to 99.5% by mole of unit X and from 0.5 to 70% by mole of unit Y, preferably from 40 to 98% by mole of unit X and of 2 to 60% by mole of unit Y, and more particularly from 50 to 90% by mole of unit X and from 10 to 50% by mole of unit Y.
  • the copolyamide according to the invention has a viscosity in the molten state measured according to standard ASTM D3236-88 (2009) of between 0.5 and 100 Pa.s at 200 ° C, preferably from 0.5 to 70 Pa.s, even more preferably from 1 to 50 Pa.s at 200 ° C, and more particularly from 2 to 30 Pa.s at 200 ° C. More particularly, the melt viscosity is measured using a Brookfield rheometer using the SC 4-27 module according to ASTM D3236-88 (2009) at 200 ° C.
  • the copolyamide according to the invention has a Tg of less than 0 ° C.
  • the noted glass transition temperature can be determined by Differential Scanning Calorimetry (DSC) according to ISO 11357-2: 2013, Plastics -Differential Scanning Calorimetry (DSC) Part 2. Heating and cooling rate are 20 ° C / min.
  • the copolyamide of the invention has a tensile modulus at 23 ° C, as measured according to the ISO 527 standard, from 5 to 240 MPa, preferably from 10 to 230 MPa, more preferably from 30 to 220 MPa, and more particularly from 65 to 200 MPa.
  • the copolyamide of the invention exhibits a threshold stress at 23 ° C, as measured according to the ISO 527 standard, from 2 to 12 MPa, preferably from 5 to 11.5 MPa and very particularly from 6 to 11 MPa.
  • the melting point of the copolyamide of the invention is preferably included in the range from 80 to 220 ° C, and in particular from 90 to 210 ° C.
  • the copolyamide comprises only the two units X and Y defined above.
  • the semi-crystalline hot-melt copolyamide according to the invention can comprise an additional unit.
  • the copolyamide according to the invention can be represented according to the following formula (2): X / Y / Z (2) in which
  • the Z unit is obtained by the polycondensation of one unit (diamine in Cf). (Cg diacid), with f representing the number of carbon atoms of the diamine and g representing the carbon number of the diacid, f being between 4 and 48 and g being between 4 and 48, the diamine in Cf being chosen by aliphatic diamines, cycloaliphatic diamines and polyetheramines,
  • copolyamide comprising from 30 to 99.5% by mole of unit X and from 0.5 to 70% by mole of units Y and Z,
  • the copolyamide according to the invention comprises at least three distinct units: the X, Y and Z units.
  • the Cf diamine can be chosen from aliphatic, linear or branched diamines and cycloaliphatic diamines, as defined above for the Ca diamine.
  • the Cf diamine can also be a polyetheramine, that is to say a polyoxyalkylene diamine.
  • a polyoxyalkylene diamine Preferably, it is a polyoxyalkylene chain carrying an amine group at the end of the chain.
  • the polyoxyalkylene chain preferably contains oxyethylene (POE), oxypropylene (POP), oxytetramethylene (POTM) groups, alone or as a mixture. When the groups are mixed, the POE and POP or alternatively POTM and POP mixtures are preferred.
  • polyetherdiols These compounds can be obtained by cyanoacetylation of aliphatic ⁇ , w-dihydroxylated polyoxyalkylene called polyetherdiols.
  • the polyetheramine is preferably chosen from commercially available products, in particular sold by Huntsman under the brands Jeffamine® and Elastamine® (for example Jeffamine® D400, D2000, ED 2003, XTJ 542, Elastamine® RT 1000, RP 405, RP 2009) or under the brand Baxxodur® by the company BASF (for example Baxxodur® EC 302, EC 301; EC 303, EC 311).
  • the number average molecular weight of the polyetheramine is between 60 and 2000 g. mol 1 , more particularly between 80 and 1500 g. mol 1 , and even more preferably between 100 and 500 g. mol 1 .
  • the Cg diacid can be chosen from aliphatic, linear or branched diacids, cycloaliphatic diacids, aromatic diacids, as defined above for Cb diacids.
  • the copolyamide according to the invention comprises at least one of the units chosen from PA 510, PA 512, PA 610, PA 612, PA6, PA11, PA 12, PA1010, PA 1012, PA 1212, PA pip36, PA pip44, PA POP40036, PA POP40044, PA PQP40010, PA POP4006, PA POP200036, PA POP200044, PA POP200010, PA POP20006, PA3636, PA3644, PA 4436, PA 4444 and their mixture.
  • the copolyamide according to the invention is chosen from the following structures: PA 510/3636, PA 512/3636, PA 510/3644, PA 512/3644, PA 510/4444, PA 512/4444, PA 610/3636, PA 612/3636, PA 610/3644, PA 612/3644, PA 610/4444, PA 612/4444, PA 1010/3636, PA 1012/3636, PA 1010/3644, PA 1012/3644, PA 1010/44, PA 1012/4444, PA 6/3636, PA 6/3644, PA 6/4444, PA 11/3636, PA 11/3644, PA 11/4436, PA 11/4444, PA 12/3636, PA 12/3644, PA 12/4444, PA 12/4444, PA 510/3636 / pip36, PA 512/3636 / pip36, PA 510/3644 / pi p44, PA 512/3644 / pi p44,
  • the Z unit comprises piperazine.
  • the Z unit is chosen from the following units PA pip36, PA pip44, PA pip10, PA 536, PA 544, PA 636, PA 644, PA POP40036, PA POP40044, PA POP200036, PA POP200044, PA POP4006, PA POP20006, PA POP200010, PA POP40010.
  • the copolyamide according to the invention comprises an X unit chosen from an amino acid and a lactam, a Y unit and a Z unit comprising piperazine as Cf diamine and a diacid comprising more than 6 carbon atoms as a C8 diacid.
  • the C-diacid and C8-diacid are C36 or C44 acid dimers.
  • the copolyamide according to the invention comprises an X-type unit (diamine in Ca). (Cb diacid) comprising an average number of carbon atoms per nitrogen atom greater than or equal to 10, a Y unit and a Z unit comprising piperazine as Cf diamine and a diacid comprising more than 6 atoms of carbon as C8 diacid.
  • the copolyamide according to the invention is chosen from PA 6/3636, PA 11/3636, PA 12/3636 and PA 11/3636 / pip36.
  • the copolyamide of the invention preferably comprises a content of between 1 and 35% by mole, in particular between 2 and 30% by moles, and very particularly between 7 and 25% by moles of fatty acid dimers.
  • the copolyamide of the invention preferably comprises polyether diamines in a content of between 0.5 and 25% by moles and in particular between 1 and 22% by moles and very particularly between 1.5 and 14% by moles per relative to the total number of moles of the components of the copolyamide.
  • the copolyamide also optionally comprises piperazine in a content of between 0 and 18 mol% relative to the total number of moles of the components of the copolyamide.
  • the copolyamide according to the invention is obtained exclusively from monomers comprising acid, amine or alcohol functions.
  • the copolyamide also advantageously comprises mainly carboxylic acid chain ends.
  • the copolyamide according to the invention comprises from 30 to 99% by mole of unit X, from 0.5 to 69.5% by mole of unit Y and from 0.5 to 69.5% by mole of unit Z ; preferably from 50 to 98% by mole of unit X, from 1 to 49% by mole of unit Y and from 1 to 49% by mole of unit Z.
  • the molar percentages of the units X, Y and optionally Z are calculated by calculating the percentage of the number of moles of monomers constituting the unit X for example relative to the sum of the numbers of moles of all the monomers constituting the copolyamide , that is to say X, Y and possibly Z, when it is present, and this excluding the chain limiter: the diamine or the diacid in excess is not counted.
  • the following formula illustrates the calculation:
  • the copolyamide comprises only the three units X, Y and Z defined above. According to this embodiment, the copolyamide consists of one or more different X units, one or more different Y units and one or more different Z units.
  • copolyamides of the invention are synthesized in a conventional manner, in the presence, if necessary, of a chain limiter or chain terminating agents.
  • Appropriate chain terminators for reacting with the amino terminal function can be monocarboxylic acids, anhydrides, such as phthalic anhydride, monohalogen acids, monoesters or monoisocyanates.
  • monocarboxylic acids are used. They can be chosen from aliphatic monocarboxylic acids, such as acetic acid, propionic acid, lactic acid, valeric acid, caproic acid, capric acid, lauric acid, acid.
  • tridecylic myristic acid, palmitic acid, stearic acid, pivalic acid and isobutyric acid; alicyclic acids, such as cyclohexanecarboxylic acid; aromatic monocarboxylic acids; such as benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid, b-naphthalenecarboxylic acid, methylnaphthalene carboxylic acid and phenylacetic acid; and their mixtures.
  • the preferred compounds are aliphatic acids, and in particular acetic acid, propionic acid, lactic acid, valeric acid, caproic acid, capric acid, lauric acid, tridecylic acid, myristic acid, palmitic acid and stearic acid.
  • chain terminating agents suitable for reacting with the acid terminal function mention may be made of monoamines, monoalcohols and monoisocyanates.
  • monoamines are used. They can be chosen from aliphatic monoamines, such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, laurylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic amines, such as cyclohexylamine and dicyclohexylamine; aromatic monoamines, such as aniline, toluidine, diphenylamine and naphthylamine; and their mixtures.
  • aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, laurylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine
  • alicyclic amines such as
  • the preferred compounds are butylamine, hexylamine, octylamine, decylamine, laurylamine, stearylamine, cyclohexylamine and aniline.
  • the chain limiters can also be a dicarboxylic acid, which is introduced in excess relative to the stoichiometry of the diamine (s); or else a diamine which is introduced in excess relative to the stoichiometry of the diacid (s).
  • a subject of the invention is also the process for preparing the copolyamide according to the invention.
  • a suitable reactor equipped with a mixer all the reagents are charged and then heated under nitrogen at a temperature between 190 ° C and 250 ° C for 20 to 180 minutes (until the volume of distillate no longer increases under nitrogen sweep). Then, the reactor is placed under vacuum at a pressure between 0.5 and 300 mBar and maintained under these conditions until the desired viscosity is obtained.
  • the present invention relates to a composition comprising a copolyamide as defined above.
  • composition defined above further comprises additives chosen from antioxidants, UV stabilizers, thermal stabilizers, plasticizers, nucleating agents, tackifiers, impact modifiers, flame retardants, agents. antistatic agents, reinforcing agents, lubricants, organic and inorganic fillers, optical brighteners, release agents, pigments, dyes, catalysts and their mixtures.
  • additives chosen from antioxidants, UV stabilizers, thermal stabilizers, plasticizers, nucleating agents, tackifiers, impact modifiers, flame retardants, agents. antistatic agents, reinforcing agents, lubricants, organic and inorganic fillers, optical brighteners, release agents, pigments, dyes, catalysts and their mixtures.
  • composition exclusively comprises compounds with an acid, amine or alcohol function.
  • composition does not contain isocyanate or urethane compounds.
  • composition of the invention does not include an alkaline catalyst. Indeed, this type of catalyst can affect chemical resistance.
  • the composition according to the invention can be used to produce molded parts which can be produced by known methods, for example by extrusion, casting molding, injection molding, compression molding, transfer molding, etc.
  • the composition is transformed into molded parts by low pressure injection molding.
  • This injection molding cycle can comprise the following different steps: a) the mold is closed after the parts to be bonded have been inserted, b) the molten composition according to the invention is injected into the mold up to a pressure of between 0.5 and 50 bar and optionally subjected to a holding pressure, c) the molding composition is allowed to solidify by cooling, d) the mold is opened, e) the injection molded parts are removed from the mold.
  • the low pressure injection molding process generally operates in the range of 2 to 40 bar, the temperature being between 160 and 250 ° C.
  • composition according to the invention is suitable for injection at low pressure, that is to say at a pressure less than 100 bars, preferably less than 50 bars.
  • the present invention relates to the use of copolyamide as defined above for the encapsulation of electronic devices, also called overmolding or molding, preferably located under the bonnet of a vehicle or in medical devices.
  • the present invention also relates to the use of at least copolyamide as defined above for the manufacture of a hot-melt adhesive, in particular a veil, a film, granules, a filament, a grid, a powder or suspension.
  • FIG.1 represents the curves obtained following the tensile test carried out on alters formulated from copolyamides according to the invention and a comparative material. On the x-axis, the percentage of strain is shown and on the y-axis, the stress expressed in MPa is shown.
  • Amino acid-11 refers to 11-aminoundecanic acid. 36 denotes, when it is in the first position, the diamine dimer.
  • Pripol 1013 ® is marketed by Croda and means the dimer acid C36.
  • Priamine ® 1074 is marketed by the company Croda and denotes the C36 amine dimer.
  • Jeffamine ® D 2000 is marketed by Huntsman and designates a polyoxypropylene diamine of molecular weight 2000 g. mob
  • Example A is a comparative copolyamide
  • Examples B to D are copolyamides according to the invention.
  • the Tg is measured by differential scanning calorimetry (DSC) according to standard ISO 11357-2: 2013, Plastics -Differential Scanning Calorimetry (DSC) Part 2.
  • the heating and cooling rates are 20 ° C./min. .
  • melt viscosity is measured using a Brookfield rheometer using the SC 4-27 module according to ASTM D3236-88 (2009) at 200 ° C. [0111] 2. Preparation of samples
  • the copolymers synthesized were ground.
  • the granules obtained were processed by compression using a Darragon plate press heated to 220 ° C. and a mold for making plates of 100 cm 2 having a thickness of 2 mm.
  • the following protocol was used: 1 min of compression at 220 ° C at 1 bar,
  • the aging of the samples in a brake fluid is evaluated.
  • the samples are placed in DOT 5.1 brake fluid at 80 ° C. for 24 hours.
  • the swelling of each sample is then measured by making the difference between the mass of the dumbbell measured before aging and the mass of the dumbbell measured after aging.
  • the aged 1 BA dumbbells are wiped so that no liquid remains on the surface of the sample. The results of the swelling test are reported below. [0117] [Table 3]
  • dumbbell formulated with comparative copolyamide A and a dumbbell formulated with copolyamide D according to the invention were soaked in different liquids and then aged without having been shaken or wiped at different temperatures for 22 hours (as recommended by the ISO standard 16740-5: 2010 (E) for the testing of electrical and electronic equipment for road vehicles):
  • +++ denotes a loss percentage of less than 30%
  • the dumbbell formulated with the copolyamide according to the invention leads to better results, whatever the liquid tested, compared to the results obtained with the comparative dumbbell.
  • the copolyamide according to the invention is more resistant to aggressive liquids. The mechanical properties are retained after aging.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Polyamides (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP21732383.1A 2020-04-17 2021-04-16 Adhésif thermofusible résistant aux fluides automobiles Pending EP4136135A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR2003895A FR3109385B1 (fr) 2020-04-17 2020-04-17 Adhésif thermofusible résistant aux fluides automobiles
PCT/FR2021/050680 WO2021209730A2 (fr) 2020-04-17 2021-04-16 Adhésif thermofusible résistant aux fluides automobiles

Publications (1)

Publication Number Publication Date
EP4136135A2 true EP4136135A2 (fr) 2023-02-22

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Country Status (4)

Country Link
EP (1) EP4136135A2 (zh)
CN (1) CN115943176A (zh)
FR (1) FR3109385B1 (zh)
WO (1) WO2021209730A2 (zh)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5978235A (ja) * 1982-10-28 1984-05-07 Ube Ind Ltd ポリアミドの製法
EP1013694A1 (en) * 1998-12-21 2000-06-28 Henkel Kommanditgesellschaft auf Aktien Hotmelt adhesives based on polyamides
DE10040762A1 (de) 2000-08-19 2002-03-07 Henkel Kgaa Formteile aus Dimerfettsäurefreie Polyamiden
JP2002356552A (ja) * 2001-05-29 2002-12-13 Nitta Gelatin Inc ポリアミド系ホットメルト組成物
US7160979B2 (en) 2003-11-24 2007-01-09 Henkel Corporation Polyamides
US7163996B2 (en) 2003-11-24 2007-01-16 Henkel Corporation Polyamides
EP2094802B1 (de) 2006-11-29 2012-11-21 Henkel AG & Co. KGaA Formteile aus schmelzklebstoffen
WO2009094127A2 (en) 2008-01-21 2009-07-30 Henkel Corporation Polyamides
EP2298830B1 (de) 2009-09-18 2011-11-09 Henkel AG & Co. KGaA Hydrolysestabile Polyamide
FR3023294B1 (fr) * 2014-07-01 2018-07-13 Arkema France Polyamides a base d'aminoalkyl- ou aminoaryl- piperazine pour adhesifs thermofusibles

Also Published As

Publication number Publication date
FR3109385B1 (fr) 2022-12-16
CN115943176A (zh) 2023-04-07
WO2021209730A2 (fr) 2021-10-21
WO2021209730A3 (fr) 2021-12-09
FR3109385A1 (fr) 2021-10-22

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