CN116096783A - Automotive fluid resistant hot melt adhesive - Google Patents
Automotive fluid resistant hot melt adhesive Download PDFInfo
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- CN116096783A CN116096783A CN202180042216.2A CN202180042216A CN116096783A CN 116096783 A CN116096783 A CN 116096783A CN 202180042216 A CN202180042216 A CN 202180042216A CN 116096783 A CN116096783 A CN 116096783A
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- 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
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- 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
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- 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
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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- 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
Abstract
The present invention relates to a semi-crystalline copolyamide comprising at least two units corresponding to the formula: X/Y, wherein-unit X is a crystalline unit obtained by polycondensation of units selected from the group consisting of C6 to C12 α, ω -aminocarboxylic acids, C6 to C12 lactams and units (Ca diamine), (Cb diacid), wherein a represents the number of carbon atoms of the diamine and b represents the number of carbon atoms of the diacid, a represents the number of carbon atoms of the diamine and is greater than 6, and b represents the number of carbon atoms of the diacid and is greater than or equal to 6, -unit Y is a unit obtained by polycondensation of units (Cd diamine), (Ce diacid), wherein D represents the number of carbon atoms of the diamine, and e represents the number of carbon atoms of the diacid, D is between 4 and 48, and e is between 6 and 48, cd diamine is selected from the group consisting of aliphatic diamines, cycloaliphatic diamines and polyethers with amine chain end-capping, -copolyamides are free of ethylenediamine, -copolyamides comprise 30 to 98mol% of units X and 2 to 70mol% of units Y, -the melt viscosity of copolyamides measured at 200 ℃ is 0.5 to 100pa s according to ASTM D3236-88 (2009). The invention also relates to a method for the production thereof and to the use thereof.
Description
The present invention relates to copolyamides for encapsulating electronic devices, to a process for preparing such copolyamides, to compositions comprising same and to their use.
It is known to use polyamides as hot melt adhesives for packaging electronic devices used in the automotive field, such as automotive engines or the medical field. Such encapsulation needs to be carried out at low pressure in order not to damage the parts to be formed.
In addition, such adhesives have the function of protecting the equipment from the environment in which they are located. It may come into contact with brake fluid, engine oil, gasoline, diesel fuel, kerosene, alcohol, battery fluid or even cooling fluid. These fluids are known to be very corrosive, especially at high temperatures, especially during engine operation. Currently, automotive engines are in an increasingly closed environment. The temperature of the air surrounding the engine may rise for efficiency and noise reasons. Higher temperatures tend to increase the temperature of the liquids, making them more corrosive to the materials with which they come into contact. These liquids are particularly susceptible to oxidation, hydrolysis and degradation under the action of relatively high temperatures. This generally results in the formation of peroxides which decompose into free radicals which themselves can attack the polymeric materials of the automotive parts which come into contact with the liquid. It is therefore necessary to increase the resistance to ageing for these liquids.
However, hot melt adhesives currently on the market demonstrate poor aging effects in these fluids, especially in brake fluid, engine oil, battery fluid and gasoline diesel.
The use of copolyamides with specific structures for low-pressure die applications is known from documents US2010/0282411, US2003/0173707, US2009/0291288, US2012/0175817, EP1533330 and EP 1533331.
Thus, good adhesion properties of these materials on different substrates, such as glass-filled epoxy, PA6, PBT, glass-filled PA6, PA6.6 or even metal surfaces, are sought. Good chemical resistance to the above-mentioned liquids, in particular good resistance to thermal ageing, good mechanical properties and finally satisfactory low-pressure injection molding processability, are also sought.
Thus, there is a need to provide polymers that combine all of these above properties.
Disclosure of Invention
The present invention relates to a semi-crystalline hot melt copolyamide comprising at least two units corresponding to the following formula (1):
X/Y(1)
wherein the method comprises the steps of
Unit X is a crystalline unit obtained by polycondensation of units selected from the group consisting of C5 to C12 alpha, omega-aminocarboxylic acids, C6 to C12 lactams and units (Ca diamine) (Cb diacid), a represents the number of carbon atoms of the diamine and is greater than 6, and b represents the number of carbon atoms of the diacid and is greater than or equal to 6,
unit Y is a unit obtained by polycondensation of units (Cd diamine) (Ce diacid), wherein d represents the number of carbon atoms of the diamine, e represents the number of carbon atoms of the diacid, d is between 4 and 48, and e is between 6 and 48, cd diamine being selected from aliphatic diamines, cycloaliphatic diamines and polyethers having amine chain terminals,
the copolyamide is free of ethylenediamine and,
copolyamides comprising 30 to 99.5mol% of units X and 0.5 to 70mol% of units Y,
the copolyamide has a melt viscosity of 0.5 to 100Pa.s measured at 200℃according to standard ASTM D3236-88 (2009),
t of copolyamide g Below 0 ℃.
The invention also relates to a process for the preparation of copolyamides according to the invention.
The invention also relates to a composition comprising the copolyamide according to the invention.
The final object of the present invention is the use of copolyamide or a composition comprising it for encapsulating electronic devices.
Detailed Description
In the following description, the invention is described in a non-limiting manner and in more detail.
By hot melt, it is meant within the meaning of the present invention the ability of the copolyamide to melt under the action of heat.
The term "semi-crystalline copolyamide" includes copolyamides having a glass transition temperature T g And a melting temperature T m Is described. T (T) g And T f Can be determined according to ISO 11357-2:2013 and 11357-3:2013, respectively.
The nomenclature used to define polyamides is described in the standard ISO 1874-1:1992 "plastics-Polyamide (PA) material for molding and extrusion-part 1: names ", especially page 3 (tables 1 and 2) and are well known to those skilled in the art. In the PAL label, PA represents polyamide, and L represents the number of carbon atoms of an amino acid or lactam. Thus, polyamides are obtained by polycondensation of amino acids or lactams containing L carbon atoms. In the PAMN notation, M represents the number of carbon atoms of the diamine, and N represents the number of carbon atoms of the diacid.
Throughout the description, unless otherwise indicated, all percentages given are mole percent.
The expression "between … … and … …", within the meaning of the present invention, the endpoints are included within the described ranges.
The semi-crystalline hot melt copolyamide comprises at least two units corresponding to the following formula (1):
X/Y (1)。
unit X
Unit X is a crystalline unit obtained by polycondensation of units selected from the group consisting of C5 to C12 α, ω -aminocarboxylic acids, C6 to C12 lactams and units (Ca diamine), (Cb diacid), a represents the carbon number of the diamine and is greater than 6, and b represents the carbon number of the diacid and is greater than or equal to 6.
The unit X may result from the polycondensation of one or more C5 to C12 alpha, omega-aminocarboxylic acids. Preferably, the α, ω -aminocarboxylic acid is selected from the group consisting of 7-aminoheptanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
The unit X may result from the polycondensation of one or more C6 to C12 lactams. Preferably, the lactam is selected from caprolactam, enantholactam and laurolactam.
The unit X may result from the polycondensation of one unit (Ca diamine), (Cb diacid), a representing the number of carbon atoms of the diamine and being greater than 6, b representing the number of carbon atoms of the diacid and being greater than or equal to 6. Preferably, a is between 7 and 48, in particular between 8 and 48, and very preferably between 9 and 48, and b is between 6 and 48, in particular between 8 and 48.
The Ca diamine may be selected from aliphatic diamines, linear or branched, alicyclic diamines and alkyl aromatic diamines.
When the Ca diamine is aliphatic and linear, it has the formula H 2 N-(CH 2 ) a -NH 2 It is preferably selected from the group consisting of heptanediamine (a=7), octanediamine (a=8), nonanediamine (a=9), decanediamine (a=10), undecanediamine (a=11), dodecanediamine (a=12), tridecanediamine (a=13), tetradecanediamine (a=14), hexadecanediamine (a=16), octadecanediamine (a=18), eicosanediamine (a=20), and docosanediamine (a=22).
Ca diamine may also result from amination of polymerized fatty acids, as defined below. The Ca diamine may be a C36 diamine.
When the Ca diamine is aliphatic and branched, it may contain one or more methyl or ethyl substituents on the backbone. For example, it may advantageously be selected from 2, 4-trimethyl-1, 6-hexamethylenediamine, 2, 4-trimethyl-1, 6-hexamethylenediamine, 2-methyl-1, 8-octanediamine.
When Ca diamine is an alkylaromatic hydrocarbon, it may be selected from 1, 3-xylylenediamine and 1, 4-xylylenediamine.
Cb diacid may be selected from aliphatic diacid, straight or branched chain, alicyclic diacid, aromatic diacid.
Throughout the description, "diacid" or "carboxylic diacid" or "dicarboxylic acid" means the same product.
When Cb diacid is aliphatic, it may be selected from adipic acid (b=6), pimelic acid (b=7), suberic acid (b=8), azelaic acid (b=9), sebacic acid (b=10), undecanedioic acid (b=11), dodecanedioic acid (b=12), brassylic acid (b=13), tetradecanedioic acid (b=14), hexadecanedioic acid (b=16), octadecanedioic acid (b=18), octadecendioic acid (b=18), eicosanedioic acid (b=20), docosanedioic acid (b=22), and dimers of fatty acids.
When the diacid is cycloaliphatic, it may comprise the following carbon backbones: norbornyl, cyclohexyl, dicyclohexyl propane.
When the diacid is aromatic, it is selected from terephthalic acid (denoted as T), isophthalic acid (denoted as I) and naphthalene diacid.
Preferably, unit X is selected from caprolactam, enantholactam and laurolactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, PA1010, PA1012, PA1014, PA1018, PA1210, PA1212, PA1214, PA1218. More particularly, unit X is selected from caprolactam, 11-aminoundecanoic acid, laurolactam, PA1012 and PA 1010.
Unit Y
The unit Y is a unit obtained by polycondensation of the unit (Cd diamine) (Ce diacid), d represents the number of carbon atoms of the diamine, e represents the number of carbon atoms of the diacid, d is between 4 and 48, e is between 6 and 48, and Cd diamine is selected from aliphatic diamines, cycloaliphatic diamines and amine chain-terminated polyethers.
The Cd diamines may be aliphatic and linear. It is then selected from butanediamine (d=4), pentanediamine (d=5), hexanediamine (d=6), heptanediamine (d=7), octanediamine (d=8), nonanediamine (d=9), decanediamine (d=10), undecanediamine (d=11), dodecanediamine (d=12), tridecanediamine (d=13), tetradecanediamine (d=14), hexadecanediamine (d=16), octadecanediamine (d=18), octadecenediamine (d=18), eicosanediamine (d=20), and docosanediamine (d=22).
Cd diamine may also result from the amination of polymeric fatty acids, as defined below. The Cd diamine may be a C36 diamine.
Cd diamines may be cycloaliphatic. It may be selected 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), isophoronediamine (d=10), piperazine (d=4) hereinafter referred to as pip, aminoethylpiperazine. It may also comprise the following carbon skeleton: norbornylmethane, cyclohexylmethane, dicyclohexylpropane, di (methylcyclohexyl) propane. A non-exhaustive list of these cycloaliphatic diamines is given in document "Cycloaliphatic Amines (cycloaliphatic amine)" (encyclopedia of chemical technology, kirk-Othmer, 4 th edition (1992), pages 386-405).
The Cd diamine may also be a polyetheramine, i.e., a polyoxyalkylene diamine. Preferably, it is a polyoxyalkylene chain having an amino group at the chain end. The polyoxyalkylene chain preferably comprises, alone or in combination, ethylene oxide (POE), propylene Oxide (POP), tetramethylene oxide (pots) groups. When these groups are mixed, preference is given to mixtures of POE and POP or even POTM and POP.
These compounds can be obtained by cyanoacetylation of aliphatic alpha, omega-dihydroxypolyalkylene oxides (known as polyether diols). The polyetheramine is preferably selected from commercially available products, in particular from Huntsman
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D400、D2000、ED2003、XTJ 542、/>
RT 1000, RP 405, RP 2009) or +.>
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EC 302、EC 301；EC 303、EC 311)。
Preferably, the polyetheramine has a number average molecular weight of 60 to 2000g.mol -1 Between, more particularly between 80 and 1500 g.mol -1 Between, and even more preferablyGround is between 100 and 500 g.mol -1 Between them.
Preferably, unit Y comprises polyetheramine.
Ce diacid may be selected from aliphatic diacids, straight or branched chain, cycloaliphatic diacids.
When Ce diacid is aliphatic, it may be selected from adipic acid (e=6), pimelic acid (e=7), suberic acid (e=8), azelaic acid (e=9), sebacic acid (e=10), undecanedioic acid (e=11), dodecanedioic acid (e=12), brassylic acid (e=13), tetradecanedioic acid (e=14), hexadecanedioic acid (e=16), octadecanedioic acid (e=18), octadecendioic acid (e=18), eicosanedioic acid (e=20), docosanedioic acid (e=22), and dimers of fatty acids.
Polymerized fatty acid refers to compounds resulting from coupling reactions of unsaturated fatty acids that result in a mixture of products with two acid functions (known as acid dimers) or three acid functions (known as acid trimers). The polymerized fatty acid is commercially available, and in particular, a polymerized fatty acid sold by Croda company under the trade name
Has the trade name +.>
Or sold by Kraton under the trade name
Or sold by Oleon company under the trade name +.>
Is a product of (a).
After separation, mainly 75% to more than 98% of the fatty acid dimer is obtained, in particular in a mixture with monomers, 11/2-mers and the corresponding trimers. Thus, depending on the purity of the commercial product used, the final copolyamide may contain in its structure a very small amount of polycondensation product of units X, cd diamine and monomers or trimers of Ce diacid present in the dimer mixture
The fatty acid dimer can then be converted to an amino dimer (by converting two acid functions to amine functions) or to an amino acid dimer (by converting one of the acid functions to an amine function).
Preferably, the diacid used for unit Y is an acid dimer, more particularly a dimer using C36 and C44.
When Ce diacid is cycloaliphatic, it may comprise the following carbon backbone: norbornyl, cyclohexyl, dicyclohexyl propane.
Preferably, unit Y is selected from PA pip36, PA pip44, PAPOP 40036, PA POP4006, PA POP40044, PA POP200036, PA POP20006, PA POP200044.POP400 represents a number average molecular weight of 400g.mol -1 Polyoxypropylene diamine of (a).
When Ce diacid is cycloaliphatic, it may comprise the following carbon backbone: norbornyl, cyclohexyl, dicyclohexyl propane.
Preferably, unit Y comprises as Ce diacid a diacid comprising more than 9 carbon atoms.
According to a preferred embodiment, unit Y comprises polyetheramine or piperazine and a diacid containing more than 9 carbon atoms as Ce diacid.
According to a preferred embodiment, unit X is selected from the group consisting of 11-aminoundecanoic acid, caprolactam, laurolactam, PA1010, PA1012 and PA1014 and unit Y comprises polyetheramine and/or piperazine as Cd diamine and diacids having more than 6 carbon atoms as Ce diacid. .
The molar mass of the units Y is preferably in the range from 200 to 3000g/mol, in particular 250 to 2500g/mol, more preferably 300 to 2250g/mol and especially 330 to 1000g/mol.
According to the invention, the copolyamide is free of ethylenediamine. Indeed, the inventors have observed that the presence of ethylenediamine reduces the chemical resistance of the material. This diamine appears to be involved in the expansion of the material in hot corrosive liquids.
The copolyamide of the invention preferably comprises fatty acid dimers in an amount of 1 to 35mol%, in particular 2 to 30mol%, most in particular 7 to 25 mol%.
Furthermore, the copolyamide of the invention preferably comprises polyetherdiamines in an amount of 0.5 to 25mol%, in particular 1 to 22mol%, most in particular 1.5 to 14mol%, relative to the total moles of copolyamide moieties.
The copolyamide may also comprise piperazine in an amount of 0 to 30mol%, in particular 0 to 22mol%, relative to the total moles of copolyamide moieties.
Advantageously, the copolyamide according to the invention exclusively comes from monomers comprising acid, amine or alcohol functions. In addition, copolyamides predominantly advantageously comprise carboxylic acid chain ends.
The copolyamide according to the invention comprises 30 to 99.5mol% of units X and 0.5 to 70mol% of units Y, preferably 35 to 95mol% of units X and 5 to 65mol% of units Y, more particularly 40 to 90mol% of units X and 10 to 60mol% of units Y.
The mole percentages of units X, Y and optionally Z are calculated by calculating the percentage of the moles of monomers constituting unit X, for example with respect to the sum of the moles of all monomers constituting the copolyamide, i.e. X, Y and optionally Z, when present, and excluding chain limiter: excess diamine or diacid is not counted. The following formula illustrates the calculation process:
[ formula 1]
The copolyamide according to the invention has a viscosity in the molten state, measured at 200 ℃, of 0.5 to 100pa.s, preferably 0.5 to 70pa.s, more preferably 1 to 50pa.s at 200 ℃, more particularly 2 to 30pa.s at 200 ℃, according to ASTM D3236-88 (2009). More specifically, the viscosity in the molten state is measured at 200℃by means of a Brookfield rheometer using an SC 4-27 module according to the standard ASTM D3236-88 (2009).
The copolyamide according to the invention has a temperature Tg of less than 0 ℃. The above noted glass transition temperatures Tg are determined by Differential Scanning Calorimetry (DSC) according to the standard ISO 11357-2:2013, section 2 of Plastic-Differential Scanning Calorimetry (DSC). The heating and cooling rates were 20 c/min.
Advantageously, the copolyamide of the invention has a tensile modulus at 23 ℃ of from 5 to 240MPa, preferably from 10 to 223MPa, more preferably from 30 to 220MPa, and most particularly from 65 to 200MPa, measured according to ISO 527 standard.
Preferably, the copolyamide according to the invention has a threshold stress at 23 ℃ of 4 to 12MPa, preferably 5 to 11.5MPa, more particularly 6 to 11MPa, measured according to standard ISO 527.
The copolyamide according to the invention preferably has a melting temperature, measured by Differential Scanning Calorimetry (DSC) using a heating rate of 20℃per minute, in the range from 80 to 220℃and in particular from 90 to 210℃according to standard NF EN ISO 11 357-3.
According to one embodiment of the invention, the copolyamide comprises only the two units X and Y defined above.
According to another embodiment, the semi-crystalline hot melt copolyamide according to the invention may comprise an additional unit. The copolyamide according to the present invention can be represented by the following formula (2):
X/Y/Z (2)
wherein the method comprises the steps of
The unit X is as previously defined,
the unit Y is as previously defined,
unit Z is a unit obtained by polycondensation of units (Cf diamine) (Cg diacid), wherein f represents the number of carbon atoms of the diamine, g represents the number of carbon atoms of the diacid, f is between 4 and 48 and g is between 4 and 48, cf diamine is selected from aliphatic diamines and cycloaliphatic diamines,
the copolyamide does not comprise ethylenediamine and,
copolyamides comprising 30 to 99.5mol% of units X and 0.5 to 70mol% of units Y and Z,
the copolyamide has a melt viscosity, measured at 200 ℃, of between 0.5 and 100pa.s according to standard ASTM D3236-88 (validated in 2009),
the Tg of the copolyamide is lower than 0 ℃.
In other words, the copolyamide according to the invention comprises at least three units: units X, Y and Z.
Cf diamine represents a diamine as defined above for Cd diamine. Cg diacid denotes a diacid as defined above for Ce diacid.
Preferably, the copolyamide according to the invention comprises at least one unit selected from PA pip.36, PA pip44, PA POP40036, PA POP4006, PA POP40044, PA POP200036, PA POP2000.6, PA POP200044.
Preferably, unit Z comprises a diacid containing more than 5 carbon atoms as Cg diacid.
According to a preferred embodiment, unit Z comprises polyetheramine or piperazine as Cf diamine and a diacid comprising more than 5 carbon atoms as Cg diacid.
Particularly preferably, the copolyamide according to the invention comprises units X selected from the group consisting of amino acids and lactams, units Y comprising polyetheramine as Cd diamine and diacids comprising at least 6 carbon atoms as Ce diacid, units Z comprising piperazine as Cf diamine and diacids comprising at least 6 carbon atoms as Cg diacid.
According to another preferred embodiment, ce diacid and Cg diacid are C36 acid dimers.
According to a preferred embodiment, the Cd diamine is a polyetheramine, the Cf diamine is piperazine, the Ce diacid and the Cg diacid are C36 acid dimers.
In a particularly preferred manner, the copolyamide according to the invention comprises units X selected from the group consisting of amino acids and lactams, units Y comprising polyetheramine as Cd diamine and diacids comprising 36 carbon atoms as Ce diacid, and units Z comprising piperazine as Cf diamine and diacids comprising 36 carbon atoms as Cg diacid.
The copolyamide according to the invention comprises 30 to 99mol% of units X, 0.5 to 69.5mol% of units Y and 0.5 to 69.5mol% of units Z; preferably 50 to 97mol% of units X, 1.5 to 48.5mol% of units Y and 1.5 to 48.5mol% of units Z.
According to another preferred embodiment, the copolyamide according to the invention does not contain amines of less than 7 carbon atoms, except piperazine.
Preferably, the copolyamide according to the invention comprises at least one unit selected from PA6, PA11, PA1010, PA1012, PA12, PA pip36, PA pip44, PA POP40036, PA POP40010, PA POP4006 and mixtures thereof.
Preferably, the copolyamide according to the invention is selected from the following structures: PA6/Pip36, PA 11/Pip36, PA 12/Pip36, PA 1010/Pip36, PA 1012/Pip36, PA6/POP40036, PA11/POP40036, PA 12/POP40036, PA 1010/POP40036, PA 1012/POP40036, 6/POP4006, PA11/POP 4006, PA 12/POP4006, PA 1010/POP4006, PA 1012/POP4006, PA6/POP 40010, PA11/POP 40010, PA 12/POP40010, PA 1010/POP40010, PA 1012/POP40010, PA6/Pip 36/POP40036, PA 11/Pip 40036/POP 40036, PA 1012/Pip 40036/POP 40036, PA6/POP 40010, PA11/POP 40010/Pip10, PA 12/POP 40010/40010, PA 1010/POP 40010/40010, PA 12/400/Pip 12/40010. Even more preferably, the copolyamide according to the invention is selected from the group consisting of PA11/POP40036/pip36, PA6/POP40036/pip36, PA11/POP200036/pip36 and PA6/POP200036/pip36.
According to one embodiment of the invention, 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 units X, one or more different units Y and one or more different units Z.
Chain limiter:
the copolyamides according to the invention are synthesized in a customary manner, if appropriate with chain limiter or chain terminator.
Chain terminators suitable for reaction with the amine terminal functional groups may be monocarboxylic acids, anhydrides, such as phthalic anhydride, monohaloacids, monoesters or monoisocyanates.
Preferably, monocarboxylic acids are used. They may be selected from aliphatic monocarboxylic acids such as acetic acid, propionic acid, lactic acid, valeric acid, caproic acid, capric acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid and isobutyric acid; alicyclic acids such as cyclohexane carboxylic acid; aromatic monocarboxylic acids; such as benzoic acid, toluic acid, alpha-naphthoic acid, beta-naphthoic acid, methylnaphthoic acid, phenylacetic acid, and the like, and mixtures thereof. Preferred compounds are fatty acids, 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.
Among the chain terminators suitable for reaction with the acid end functions, mention may be made of monoamines, monoalcohols, monoisocyanates.
Preferably monoamines are used. They may be selected 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, naphthylamine, and the like; and mixtures thereof.
Preferred compounds are butylamine, hexylamine, octylamine, decylamine, laurylamine, stearylamine, cyclohexylamine and aniline.
The chain limiter may also be a dicarboxylic acid, which is introduced in stoichiometric excess with respect to the diamine or diamines; or diamines, which are introduced in stoichiometric excess with respect to the diacid or diacids.
The preparation method comprises the following steps:
the invention also relates to a method for producing the copolyamide according to the invention. In a suitable reactor equipped with a mixer, all reagents were loaded and then heated under nitrogen at a temperature of 190 to 250 ℃ for 20 to 180 minutes (until the volume of distillate no longer increased under a nitrogen sweep). The reactor is then placed under vacuum at a pressure of 0.5 to 300mBar and maintained under these conditions until the desired viscosity is obtained.
Composition:
according to a further aspect, the present invention relates to a composition comprising a copolyamide as defined above.
Advantageously, the composition defined above further comprises additives selected from antioxidants, UV stabilizers, heat stabilizers, plasticizers, nucleating agents, tackifiers, impact modifiers, flame retardants, antistatic agents, reinforcing agents, lubricants, organic and inorganic fillers, optical brighteners, mold release agents, pigments, colorants, catalysts, and mixtures thereof.
Preferably the composition comprises only compounds having acid, amine or alcohol functionality. It is particularly preferred that the composition does not contain isocyanate or urethane compounds.
Advantageously, the composition of the invention does not comprise a basic catalyst. In fact, this type of catalyst may affect chemical resistance.
The composition according to the invention can be used for the manufacture of molded parts which can be produced by known methods, for example by extrusion, cast molding, injection molding, compression molding, transfer molding, etc. However, according to the invention, the composition is molded into molded parts by low pressure injection molding. The injection molding cycle may include the following different steps:
a) After the components to be bonded are inserted, the mold is closed,
b) The melted composition according to the invention is injected into a mould until the pressure is between 0.5 and 50bars and optionally undergoes a holding pressure,
c) The molded composition is allowed to cool and solidify,
d) The mold is opened and the mold is opened,
e) The injection molded part is removed from the mold.
The low pressure injection moulding process is typically operated in the range 2 to 40bars and at a temperature between 160 and 250 ℃.
The composition according to the invention can therefore be injection molded at low pressure, that is to say at a pressure of less than 100bars, preferably less than 50bars.
The application is as follows:
according to a further aspect, the invention relates to the use of a copolyamide as defined above in the packaging of an electronic device, also called over-molding or moulding, preferably under the hood of a vehicle or in a medical device.
The invention also relates to the use of at least one copolyamide as described above for producing hot melt adhesives, in particular yarns, films, granules, filaments, grids, powders or suspensions.
The invention finally relates to the use of semi-crystalline copolyamides comprising at least two units corresponding to the following formula (3):
X/Y (3)
wherein the method comprises the steps of
Unit X is a crystallization unit obtained by polycondensation of units selected from the group consisting of C5 to C12 alpha, omega-aminocarboxylic acids, C6 to C12 lactams and units (Ca diamine), (Cb diacid), wherein a represents the number of carbon atoms of the diamine and b represents the number of carbon atoms of the diacid, a and b being greater than or equal to 4,
unit Y is a unit obtained by polycondensation of units (Cd diamine) (Ce diacid), wherein d represents the number of carbon atoms of the diamine, e represents the number of carbon atoms of the diacid, d is between 4 and 48, e is between 6 and 48, cd diamine is selected from aliphatic diamines, cycloaliphatic diamines and amine chain terminated polyethers,
the copolyamide is free of ethylenediamine and,
copolyamides comprising 30 to 99.5mol% of units X and 0.5 to 70mol% of units Y,
the copolyamide has a melt viscosity, measured at 200 ℃, of between 0.5 and 70pa.s according to standard ASTM D3236-88 (validated in 2009),
the Tg of the copolyamide is lower than 0 ℃,
hot melt adhesives for use in the manufacture of automotive fluids result in improved chemical resistance of the materials after heat aging.
It has been shown that copolyamides of formula (3) have good adhesion properties on various substrates, such as glass-fibre-filled epoxy resins, PA6, PBT, glass-fibre-filled PA6, PA6.6 and even metal surfaces, have good mechanical properties, satisfactory low-pressure injection molding processability and, above all, improved chemical resistance to automotive fluids after thermal ageing of the material.
By automotive fluid, it is meant within the meaning of the present invention brake fluid, engine oil, gasoline, such as diesel, biodiesel, battery fluid, coolant.
For improved chemical resistance after heat aging of the material, the expansion is less than 20wt%.
Preferably, unit X, Y and optionally Z, as well as other characteristics of the copolyamide are as defined above.
The invention is illustrated by the accompanying drawings and the following non-limiting examples.
Drawings
FIG. 1 shows the curves obtained after tensile test of copolyamides according to the invention and of comparative materials on dumbbell-shaped test pieces prepared. The abscissa represents deformation in percent and the ordinate represents stress in MPa.
Examples:
1.preparation of copolyamide:
the synthesis was carried out as a one-step procedure as follows. In a suitable reactor equipped with a mixer, all reagents were loaded and then heated under nitrogen at a temperature of 235 ℃ for 90 minutes. The reactor was then placed under a vacuum of 100mBar and maintained under these conditions until the desired viscosity was obtained.
The following copolyamides were prepared from the reagents listed in table 1 below.
TABLE 1
In this table:
11-amino acid means 11-aminoundecanoic acid.
DA 10 represents decamethylene diamine.
DC 10 represents sebacic acid.
Examples A and G are comparative copolyamides and examples B to F are copolyamides according to the invention.
During the synthesis according to example B of the present invention, excess sebacic acid was used as chain limiter. In the synthesis according to examples C, D, E and F of the invention, the excess
1013 act as chain limiter.
The resultant copolyamide has the following composition and characteristics.
Tg is measured by Differential Scanning Calorimetry (DSC) according to standard ISO 11357-2:2013, section 2 of plastic-Differential Scanning Calorimetry (DSC). The heating and cooling rates were 20 c/min.
Viscosity in the molten state was measured by means of a Brookfield rheometer using SC 4-27 module at 200 ℃ according to standard ASTM D3236-88 (2009).
TABLE 2
* Nd=undetermined.
2.Preparation of samples
The synthesized copolymer was ground. 100cm of the granules obtained by pressing were prepared using a Darrago flat press and die heated to 220 ℃ 2 Is a flat plate with a thickness of 2 mm.
The following scheme was used:
compressed for 1 minute at 220℃and 1bar,
compressed for 2 minutes at 220℃and 50bars,
cooled at 50bars for 4 minutes (cold water circulated in the platens).
Dumbbell specimen with the aid of the component support allows the cutting of dumbbell specimen 1BA these flat cuts (appendix a standard ISO 527-2:2012) were used for tensile testing according to standard ISO 527-2:2012.
3.Sample evaluation:
3.1.resistance to swelling:
the aging of the samples was evaluated in brake fluid. The samples were placed in DOT 5.1 brake fluid at 80 ℃ for 24 hours. The swell of each sample was then measured by taking the difference between the mass of the dumbbell specimen measured before aging and the mass of the dumbbell specimen measured after aging. To obtain reproducible results, the aged dumbbell sample 1BA was wiped dry so that no liquid remained on the sample surface. The results of the expansion test are reported in table 3 below.
TABLE 3
The results obtained show that the copolyamide according to the invention is more resistant to thermal ageing in the brake fluid than the comparative material.
3.2.Mechanical resistance:
tensile tests were performed on dumbbell sample 1BA according to standard ISO 527-2:2012 (appendix a standard ISO 527-2:2012).
The results obtained are shown in fig. 1 and table 2 above. These results show that the copolyamide according to the invention has better mechanical properties than the comparative material.
Furthermore, we note that the copolyamides of comparative examples a and G have a high modulus and high threshold stress, which is undesirable for parts over molded by low pressure injection molding. Copolyamides comprising units derived from acid dimers (examples C to F) exhibit significantly more suitable mechanical properties, so that they are significantly more suitable for this application.
Claims (14)
1. A semi-crystalline copolyamide comprising at least two units corresponding to the formula: X/Y wherein
Unit X is a crystalline unit obtained by polycondensation of units selected from the group consisting of C5 to C12 alpha, omega-aminocarboxylic acids, C6 to C12 lactams and units (Ca diamine), (Cb diacid), wherein a represents the number of carbon atoms of the diamine and is greater than 6, and b represents the number of carbon atoms of the diacid and is greater than or equal to 6,
unit Y is a unit obtained by polycondensation of units (Cd diamine) (Ce diacid), wherein d represents the number of carbon atoms of the diamine, and e represents the number of carbon atoms of the diacid, d is between 4 and 48, e is between 6 and 48, cd diamine is selected from aliphatic diamines, cycloaliphatic diamines and amine chain terminated polyethers,
the copolyamide is free of ethylenediamine and,
copolyamides comprising 30 to 99.5mol% of units X and 0.5 to 70mol% of units Y,
the copolyamide has a melt viscosity, measured at 200 ℃, of between 0.5 and 100Pa.s according to standard ASTM D3236-88 (2009),
the Tg of the copolyamide is lower than 0 ℃.
2. Copolyamide according to claim 1, characterized in that the Cd diamine is an amine chain-terminated polyether.
3. Copolyamide according to any of the preceding claims, characterized in that it comprises units X selected from 11-aminoundecanoic acid, caprolactam, laurolactam, PA1010, PA1012 and PA1014 and units Y comprising polyetheramine and/or piperazine as Cd diamine and diacids comprising more than 6 carbon atoms as Ce diacid.
4. Copolyamide according to any of the preceding claims, characterized in that it comprises an additional unit, said copolyamide then having the following formula (2):
X/Y/Z (2)
wherein the method comprises the steps of
Unit X is as defined in claim 1,
unit Y is as defined in claim 1,
unit Z is a unit obtained by polycondensation of units (Cf diamine) (Cg diacid), wherein f represents the number of carbon atoms of the diamine, g represents the number of carbon atoms of the diacid, f is between 4 and 48 and g is between 4 and 48, cf diamine is selected from aliphatic diamines and cycloaliphatic diamines,
the copolyamide is free of ethylenediamine and,
copolyamides comprising 30 to 99.5mol% of units X and 0.5 to 70mol% of units Y and Z,
the copolyamide has a melt viscosity, measured at 200 ℃, of between 0.5 and 100Pa.s according to standard ASTM D3236-88 (2009),
the Tg of the copolyamide is lower than 0 ℃.
5. Copolyamide according to any of the preceding claims, characterized in that the melt viscosity is between 0.5 and 70pa.s at 200 ℃, preferably between 1 and 50pa.s at 200 ℃, more particularly between 2 and 30pa.s at 200 ℃.
6. Copolyamide according to any of the preceding claims, characterized in that it comprises at least one unit chosen from PA6, PA11, PA1010, PA1012, PA12, PA pip36, PA pip44 POP40036, PA POP40010, PA POP4006 and mixtures thereof.
7. Copolyamide according to any of the preceding claims, characterized in that it comprises units X, selected from amino acids and lactams, units Y, comprising polyetheramine as Cd diamine and diacid comprising more than 6 carbon atoms as Ce diacid, units Z, comprising piperazine as Cf diamine and diacid comprising more than 6 carbon atoms as Cg diacid.
8. Copolyamide according to any of the preceding claims, characterized in that it has the formula: PA6/Pip36, PA 11/Pip36, PA 12/Pip36, PA 1010/Pip36, PA 1012/Pip36 PA6/POP40036, PA11/POP40036, PA 12/POP40036, PA 1010/POP40036, PA 1012/POP40036, 6/POP4006, PA11/POP 4006, PA 12/POP4006, PA 1010/POP4006, PA 1012/POP4006, PA6/POP 40010, PA11/POP 40010, PA 12/POP40010, PA 1010/POP40010, PA 1012/Pip 40010, PA 1010/Pip36/POP40036, PA 12/Pip 40036/POP 40036, PA 1010/Pip36/POP40036, PA 1012/Pip 4006/POP 40010, PA11/POP 40010/Pip 40010, PA 12/POP 40010/40010, PA 1010/400/POP 40010.
9. A composition comprising a copolyamide as defined in any one of claims 1 to 8.
10. Composition according to claim 9, characterized in that it comprises additives selected from antioxidants, UV stabilizers, heat stabilizers, plasticizers, nucleating agents, tackifiers, impact modifiers, flame retardants, antistatic agents, reinforcing agents, lubricants, organic and inorganic fillers, optical brighteners, mold release agents, pigments, colorants, catalysts and mixtures thereof.
11. Composition according to claim 9 or 10, characterized in that it is suitable for injection moulding at a pressure of less than 100bars, preferably less than 50bars.
12. Use of a copolyamide as defined in any one of claims 1 to 8 or a composition as defined in any one of claims 9 to 11 in an electronic packaging, preferably under the hood of a vehicle or in a medical device.
13. Use of a semi-crystalline copolyamide comprising at least two units corresponding to the formula:
X/Y
wherein the method comprises the steps of
Unit X is a unit crystal obtained by polycondensation of units selected from the group consisting of C6 to C12 alpha, omega-aminocarboxylic acids, C6 to C12 lactams and units (Ca diamine) (Cb diacid), wherein a represents the number of carbon atoms of the diamine and b represents the number of carbon atoms of the diacid, a and b being greater than or equal to 4,
unit Y is a unit obtained by polycondensation of units (Cd diamine) (Ce diacid), wherein d represents the number of carbon atoms of the diamine and e represents the number of carbon atoms of the diacid, d is between 4 and 48, e is between 6 and 48, cd diamine is selected from aliphatic diamines, cycloaliphatic diamines and amine chain terminated polyethers,
the copolyamide is free of ethylenediamine and,
copolyamides comprising 30 to 99.5mol% of units X and 0.5 to 70mol% of units Y,
the copolyamide has a melt viscosity, measured at 200 ℃, of between 0.5 and 70Pa.s according to standard ASTM D3236-88 (2009),
the Tg of the copolyamide is lower than 0 ℃,
hot melt adhesives for use in the manufacture of automotive fluids result in improved chemical resistance of the materials after heat aging.
14. Use according to claim 13, characterized in that the units X and Y are as defined in any one of claims 1 to 8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2003893 | 2020-04-17 | ||
| FR2003893A FR3109384B1 (en) | 2020-04-17 | 2020-04-17 | Hot melt adhesive resistant to automotive fluids |
| PCT/FR2021/050679 WO2021209729A2 (en) | 2020-04-17 | 2021-04-16 | Hot melt adhesive withstanding motor vehicle fluids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116096783A true CN116096783A (en) | 2023-05-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180042216.2A Pending CN116096783A (en) | 2020-04-17 | 2021-04-16 | Automotive fluid resistant hot melt adhesive |
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| Country | Link |
|---|---|
| EP (1) | EP4136134A2 (en) |
| CN (1) | CN116096783A (en) |
| FR (1) | FR3109384B1 (en) |
| WO (1) | WO2021209729A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10040762A1 (en) | 2000-08-19 | 2002-03-07 | Henkel Kgaa | Molded parts made from dimer fatty acid-free polyamides |
| US7163996B2 (en) | 2003-11-24 | 2007-01-16 | Henkel Corporation | Polyamides |
| US7160979B2 (en) | 2003-11-24 | 2007-01-09 | Henkel Corporation | Polyamides |
| EP2094802B1 (en) | 2006-11-29 | 2012-11-21 | Henkel AG & Co. KGaA | Molded parts from hot melt adhesives |
| ATE552288T1 (en) * | 2007-07-25 | 2012-04-15 | Ems Patent Ag | TRANSPARENT POLYAMIDE ELASTOMERS |
| WO2009094127A2 (en) | 2008-01-21 | 2009-07-30 | Henkel Corporation | Polyamides |
| US8541321B2 (en) * | 2008-05-15 | 2013-09-24 | Toyo Boseki Kabushiki Kaisha | Copolymerized polyether polyamide resin |
| EP2298830B1 (en) | 2009-09-18 | 2011-11-09 | Henkel AG & Co. KGaA | Hydrolysis stable polyamides |
| FR2992968B1 (en) * | 2012-07-06 | 2014-07-04 | Arkema France | HYDRODISPERSIBLE POLYAMIDE POWDER |
| CA2900317C (en) * | 2013-02-13 | 2019-11-19 | Lubrizol Advanced Materials, Inc. | Water borne polyamide-urea dispersions |
| CN109749695A (en) * | 2017-11-06 | 2019-05-14 | 山东凯恩新材料科技有限公司 | A kind of novel polyamide hot melt adhesive and preparation method thereof |
-
2020
- 2020-04-17 FR FR2003893A patent/FR3109384B1/en active Active
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- 2021-04-16 CN CN202180042216.2A patent/CN116096783A/en active Pending
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| Publication number | Publication date |
|---|---|
| WO2021209729A3 (en) | 2021-12-09 |
| WO2021209729A2 (en) | 2021-10-21 |
| FR3109384B1 (en) | 2023-09-01 |
| FR3109384A1 (en) | 2021-10-22 |
| EP4136134A2 (en) | 2023-02-22 |
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