Structure including flexible semi-aromatic polyamides with low moisture take-up
Abstract
Structure comprising at least one layer consisting of a composition (C) and other layers consisting of other materials, the structure comprising: - an outer layer consisting of the composition (C), - possibly a binder layer, - an inner, possibly conductive layer, consisting of aliphatic polyamine, polyolefin or a compatible mixture of aliphatic polyamine and polyolefin, - possibly a conductive layer 10 of aliphatic polyamide or of a mixture of polyamide to liftatic and polyolefin, the composition (C) comprising, by weight, the total being 100: - from 60 to 99.5% of at least one copolyamide of formula X / Y, Ar, in which: - Y represents the residues of an aliphatic diamine having 8 to 20 carbon atoms, - Ar represents the remains of an aromatic carboxylic diacid, - X represents either the amino acid amino acid residues NH2- (CH2) 10-COOH, of Lactam 12 or the corresponding amino acid, either the reason Y, x rest of the condensation of the diamine with an aliphatic diacid (x) between 8 and 20 carbon atoms, or the reason Y, I rest of the condensation of the diamine with isophthalic acid, - from 0.5 to 40% of at least one product chosen from plasticizers, nano-charges, polyolefins, cross-linked polyolefins and additives - said composition, possibly comprising an aliphatic polyamide.
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10 claims: 2 independent, 8 dependent
- 1ES 2 551 748 T3 REIVINDICACIONES 1. Estructura que comprende por lo menos una capa constituida por una composición (C) y otras capas constituidas por otros materiales, comprendiendo la estructura :- una capa externa constituida por la composición (C), - eventualmente una capa de ligante, - una capa interior, eventualmente conductora, constituida por poliamina alifática, por poliolefina o por una mezcla compatibilizada de poliamina alifática y de poliolefina, - eventualmente, una capa conductora de poliamida alifática o de una mezcla de poliamida alifática y de poliolefina, comprendiendo la composición (C), en peso, siendo el total de 100 : - de un 60 a un 99,5 % de por lo menos una copoliamida de fórmula X/Y, Ar, en la cual: - Y representa los restos de una diamina alifática que tiene de 8 a 20 átomos de carbono, - Ar representa los restos de un diácido carboxílico aromático, - X representa bien sea los restos del ácido aminoundecanoico NH2-(CH2)-iü-COOH, de la lactama 12 ó del aminoácido correspondiente, bien sea el motivo Y, x resto de la condensación de la diamina con un diácido alifático (x) entre 8 y 20 átomos de carbono, o bien sea el motivo Y, I resto de la condensación de la diamina con el ácido isoftálico, - de un 0,5 a un 40 % de por lo menos un producto escogido entre los plastificantes, las nanocargas, las poliolefinas, las poliolefinas reticuladas y los aditivos - dicha composición comprendiendo eventualmente una poliamida alifática.
- 2Estructura según la reivindicación 1, caracterizada porque, la cantidad de poliamina alifática está comprendida entre un 5 y un 40 % por respectivamente un 95 a un 60 % de copoliamida X/Y, Ar.
- 3Estructura según la reivindicación 1 ó 2, caracterizada porque, Ar representa el ácido tereftálico.
- 4Estructura según una cualquiera de las reivindicaciones 1 a 3, caracterizada porque, la diamina “Y” es una alfa omega diamina de cadena recta de 9 a 14 átomos de carbono, de preferencia la 1,10-decanodiamina.
- 5Estructura según una cualquiera de las reivindicaciones 1 a 4, caracterizada porque, la composición(C) comprende de un 70 a un 93 % en peso de por lo menos una copoliamida X/Y, Ar.
- 6Estructura según una cualquiera de las reivindicaciones 1 a 5, caracterizada porque, la composición(C) comprende de un 7 a un 30 % en peso de por lo menos un producto escogido entre los plastificantes,las nanocargas, las poliolefinas, las poliolefinas reticuladas y aditivos.
- 7Estructura según una cualquiera de las reivindicaciones 1 a 6, caracterizada porque, tiene entre 0,5 y 0,7 moles de X por 1 mol de Y (ó 1 mol de Ar).
- 8Estructura según una cualquiera de las reivindicaciones 1 a 6, caracterizada porque X/Y,Ar representa la copoliamida :- 11/10,T que resulta de la condensación del ácido aminoundecanoico, de la 1,10- decanodiamina y del ácido tereftálico, - 12 /12,T que resulta de la condensación de la lactama 12, de la 1,12-dodecanodiamina y del ácido tereftálico, - 10, 10 /10,T que resulta de la condensación del ácido sebácico, de la 1,10-decanodiamina y del ácido tereftálico, o - 10, 1/10,T que resulta de la condensación del ácido isoftálico, de la 1,10-decanodiamina y del ácido tereftálico.
- 9Estructura según una cualquiera de las reivindicaciones 1 a 8, caracterizada porque, la misma comprende :- una capa externa constituida por la composición (C), - eventualmente una capa de poliamida alifática o de una mezcla de poliamida alifática y de poliolefina, - eventualmente, una capa de ligante, ES 2 551 748 T3 - una capa central constituida esencialmente por un material barrera escogido entre el EVOH, los polímeros fluorados, el PPS, el PBN, una policetona alifática, en PA- MXD6, un LCP, los polímeros nano compósitos y una aleación que tiene por matriz uno de dichos materiales, - eventualmente, una capa de ligante, - una capa interna, eventualmente conductora, constituida por poliamida alifática, poliolefina o una mezcla compatibilizada de poliamida alifática y de poliolefina, - eventualmente, una capa conductora de poliamida alifática o de una mezcla de poliamida alifática y de poliolefina.
- 10Dispositivo de almacenamiento o de transferencia de fluidos, el cual comprende una estructura según una cualquiera de las reivindicaciones 1
Independent claims10
201 paragraphs in 10 sections, as filed
ES 2 551 748 T3
DESCRIPTION
Structure comprising flexible semi-aromatic polyamides with weak moisture absorption
[Field of the invention]
The present invention relates to flexible semi-aromatic polyamides with poor moisture absorption. These polyamides also have good elongation properties. These polyamides have a high thermomechanical resistance. Polyamides 6 and 6.6 have high melting temperatures, but their transformation is difficult, and in addition, their water absorption is too high, which penalizes their mechanical properties and their resistance to aging. In addition, they are very rigid to be used as pipes, and then it is necessary to soften them by means of plasticizers or shock modifiers. All properties are then lost. Polyamides 12 and 11 are widely used in the automotive industry due to their remarkable mechanical properties, ease of use and resistance to aging. However, beyond 160 ° C of service temperature, its thermomechanical resistance is not sufficient. The invention relates to polyamides which should replace polyamides 12 and 11, but whose thermomechanical behavior is improved, while preserving their ease of transformation and flexibility.
[Prior art and technical problem]
There are terephthalic copolyamides based on 6 (for example 6, 6/6, T or 6/6, T or even 6.1 / 6, T with most of 6, T) that have very high Tf's, for above 300 ° C. These products are very rigid and their elongation at break is less than 10%, which prevents their use in the field of tube extrusion. EP 550314 is an example of 126, T copolyamides. US patent 3 843 611 describes copolyamides 12, 12/12, T. US Pat. No. 5,708,125 describes 10.6 / 10, T copolyamides. None of these classes cited describes a possible aptitude to aging. Furthermore, none of these cited classes describes the need for flexible polyamides. The purpose of the present invention is to find polyamides that have resistance to aging when subjected to a high service temperature while remaining flexible. These compositions have now been discovered.
[Brief description of the invention]
The present invention refers to structures that comprise a layer made up of a composition (C) and other layers made up of other materials, said structure comprising:
- An outer layer made up of composition (C),
- Eventually, a layer of binder,
- An inner layer, possibly conductive, made up of aliphatic polyamide or polyolefin or a compatibilized mixture of polyamide and polyolefin,
- If necessary, a conductive layer of aliphatic polyamide or of a mixture of aliphatic polyamide and polyolefin, comprising composition (C) by weight, 100 being the total:
- 60 to 99.5% (preferably 70 to 93%) of at least one copolyamide of formula X / Y, Ar, in which:
- Y means the remains of an aliphatic diamine that has 8 to 20 carbon atoms,
- Ar means the residues of an aromatic carboxylic diacid,
- X means either the residues of the aminoundecanoic acid NH2- (CH2) 10-COOH of the lactam 12 or of the corresponding amino acid, or the motif Y, x residue of the condensation of the diamine with an aliphatic diacid (x) having between 8 and 20 carbon atoms, or the Y, I motif remainder of the condensation of diamine with isophthalic acid,
- From 0.5 to 40% (preferably 7 to 30%) of at least one product chosen from plasticizers, nano-fillers, polyolefins, cross-linked polyolefins, and additives.
- Possibly said composition containing an aliphatic polyamide.
Advantageously, the inherent viscosity of the copolyamide is between 0.5 and 2 and preferably between 0.8 and 1.8.
The advantage of these compositions is the low absorption of water, which does not exceed 3.5% and advantageously 3% by weight.
Preferably X / Y, Ar means:
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- 11/10, T which results from the condensation of aminoundecanoic acid, 1,10-decanediamine and terephthalic acid,
- 12/12, T which results from the condensation of lactam 12, 1,12-dodecanediamine and terephthalic acid,
- 10, 10/10, T, which results from the condensation of sebacic acid, 1,10 decanediamine and terephthalic acid,
- 10, l / 10, T, which results from the condensation of isophthalic acid, 1,10-decanediamine and terephthalic acid.
This structure is useful for making fluid transfer or storage devices, particularly in automobiles. The invention also relates to these devices. These devices can be tanks, pipes, vessels. These structures can comprise other layers made of other materials.
The compositions of the invention can replace rubbers or metals.
The compositions of the invention are also useful as materials for electrical cables and can replace fluorinated polymers.
The compositions of the invention are useful as materials for formulations with charges: without magnetic charges. The compositions of the invention then serve as binders for this type of filler.
It has also been discovered that adding an aliphatic polyamide in the compositions of the invention then greatly improves the thermo-oxidative content. Thermo-oxidative content is defined as life<sup>1</sup>X with an elongation break that reaches 50% of the initial elongation, that is, the time after which the elongation at break decreases by half. As an example of aliphatic polyamide, mention may be made of PA11, PA12, PA10, 10 (C10 diamine and C10 diazide), PA 12,12 (C12 diamine and C12 diazide), the copolyamides resulting from the condensation of at least two lactams (or the corresponding amino acids), the copolyamides resulting from the condensation of at least one lactam, at least one diamine and at least one diacid, as well as the aliphatic PAs resulting from the condensation of hexamethylenediamine with a C 10 to C 36 diacid (for example PA 6.10, PA 6.12, PA 6.14, and PA 6.36). It is advantageous if these polyamides are miscible with the PA X / Y, Ar mentioned above. It is also advantageous that these polyamides have a saturation water absorption of less than 3.5%.
It is advantageous if the amount of this aliphatic polyamide to be added is comprised between 5 and 40% for respectively 95 to 60% of Pa X / Y, Ar.
It is advantageous if the amount of this aliphatic polyamide that is added contains an organic or mineral catalyst that has been added, either in the course of its preparation or later. It is preferably phosphoric acid or hypophosphoric acid. The amount of catalyst can be up to 3000 ppm relative to the amount of aliphatic polyamide and it is advantageous if it is between 50 and 1000 ppm.
For example, the compositions of the invention in which the PA is 11/10, T and which contain 0.6% by weight of a thermal stabilizer of the phenol, phosphite, potassium iodide type (for example iodine 101 or 201 from Ciba specialty chemicals) have a half-life of 24 to 48 hours. If 30% PA 11 (for 70% PA X / Y, Ar) containing 600 ppm of H3PO4 is added to this composition, the half-life passes to more than 1250 hours.
[Detailed description of the invention]
When it comes to an aromatic diacid, mention can be made of terephthalic acid, isophthalic acid, bibenzoic acid, naphthalene dicarboxylic acid, 4,4'-diphenylene dicarboxylic acid, bis (p-carboxyphenyl) methane acid, ethylene bis p-benzoic acid, 1-4 tetramethylene bis (p-oxybenzoic) acid, ethylene bis (for oxybenzoic) acid, 1,3-trimethylene bis (p-oxybenzoic) acid. Preferably it is terephthalic acid, which is designated by "T".
When it comes to "Y", the diamine can be a straight chain alpha-omega diamine. Preferably it has 9 to 14 carbon atoms. According to a preferred embodiment, it is 1,10-decanediamine. It can be branched or it can be a mixture of a straight diamine (straight chain) and a branched diamine.
When it comes to "X" and more particularly "x" within "Y", "x" is advantageously a straight chain aliphatic alpha-omega diacid. It preferably has between 9 and 14 carbon atoms.
When it comes to proportions of X, Y and Ar, Y and Ar are in stoichiometric or very close proportions.
Advantageously, there are between 0.5 and 0.7 moles of X per 1 mole of Y (or one mole of Ar).
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0.5 moles of X means also 0.5 moles of Y, x, that is 0.5 moles of Y and 0.5 moles of x in the group Y, x. Similarly, 0.5 moles of X means also 0.5 moles of Y, I, that is 0.5 moles of Y and 0.5 moles of I in group Y, I.
When Y is a long chain, for example, at least on the order of 15 to 18 carbon atoms, then the proportions of X can be very weak to zero. The copolyamide is reduced to Y, Ar. The invention also relates to the preceding compositions in which X / Y, Ar has been converted to Y, Ar and Y mean the residues of an aliphatic diamine having 10 to 20 (preferably 15 to 20 and more preferably 18 to 20) carbon atoms.
If X / Y, Ar means 10.10 / 10, T, then the proportions of X can be higher and be between 0.5 moles per 1 mole of Y and 1 mole per 0.05 moles of Y.
As an exception to what has been described above, if X / Y, Ar means 10, I / 10, T then the ratio of 10.1 is higher than that of 10, T.
When it comes to a plasticizer, it is chosen from benzene sulfonamide derivatives, such as n-butyl benzene sulfonamide (BBSA), ethyl toluene sulfonamide or N-cyclohexyl toluene sulfonamide; esters of hydroxybenzoic acids, such as ethyl-2-hexyl parahydroxybenzoate and decyl-2-hexyl parahydroxybenzoate; esters or ethers of tetrahydrofurfuryl alcohol, such as oligoethylenexytetrahydrofurfuryl alcohol; esters of citric acid or hydroxymalonic acid, such as oligoethyleneoxy malonate. Mention may also be made of decyl hexyl parahydroxybenzoate and ethylhexylparahydroxybenzoate. A particularly preferred plasticizer is n-butyl benzene sulfonamide (BBSA).
When it comes to nanocharges, they are called like this, particles of any shape, of which at least one of their dimensions is of the order of a nanometer. Advantageously, they are exfoliating lamellar fillers. In particular, the exfoliable lamellar fillers are silicates and especially organophilic treated clays; These clays, which appear in the form of small sheets, become organophilic by intercalation of organic molecules or polymers, and are obtained in particular according to a process as described in US Pat. No. 5,578,672.
Preferably, the clays used are of the smectite type, either of natural origin such as montmorillonites, bentonites, saponites, hectorites, fluorohectorites, beidellites, stibensites, nontronites, stipulgites, attapulgites, illites, vermiculites, halosites, stevensites, zeolites, fuller's earths and mica, well they are, of synthetic origin such as permutites.
By way of example, mention may be made of the organophilic clays mentioned in US patent 6117932. Preferably, the clay is modified with an organic substance by ionic bonding with an onium ion of 6 or more carbon atoms. If the number of carbon atoms is less than 6, the organic onium ion is too hydrophilic and then the compatibility with the polymer (the mixture of (A) and (B)) may decrease. By way of an example of an organic onium ion, mention may be made of hexylammonium ions, octylammonium ions, 2-ethylhexylammonium ions, dodecylammonium ions, laurylammonium ions, octadecylammonium (stearylammonium) ions, dioctyldimethylammonium ions, trioctyldimethylammonium ions, distearyldimethylammonium ions, stearyltrimethylammonium ions, and ammonium laurate ions. It is recommended to use a clay with the largest possible contact surface with the polymer. The larger the contact surface, the more important the separation of the clay flakes will be. The cation exchange capacity of the clay is preferably between 50 and 200 milliequivalents per 100 g. If the capacity is less than 50, the onium ion exchange is insufficient and the separation of the clay flakes may be difficult. On the contrary, if the capacity is greater than 200, the bonding force between the clay flakes is so strong that the separation of the flakes may be difficult. As an example of clay, mention may be made of smectite, montmorillonite, saponite, hectorite, beidellite, stibensite, nontronite, vermiculite, hallosite and mica. These clays can be of natural or synthetic origin. The proportion of the organic onium ion is advantageously between 0.3 and 3 equivalents of the ionic exchange capacity of the clay. If the ratio is less than 0.3, the separation of the clay flakes may be difficult. If the ratio is greater than 3, degradation of the polymer may occur. The proportion of organic onium ion is preferably between 0.5 and 2 equivalents of the ion exchange capacity of the clay. The nanofillers can be added to the monomers and be present during the polymerization of the copolyamide or they can be added after polymerization.
When it comes to cross-linked polyolefins, this phase can come from, (i) the reaction of two polyolefins with reactive groups with each other, (ii) difficult polyolefins, with a monomeric, oligomeric or polymeric diamino molecule, (iii), of a (or more) unsaturated polyolefins that carry unsaturation and are crosslinkable, for example by peroxide. When it comes to the reaction of two polyolefins, this cross-linked phase comes for example from the reaction:
- of a product (A) comprising an unsaturated epoxide
- of a product (B) comprising an unsaturated carboxylic acid anhydride
ES 2 551 748 T3
- optionally, a product (C) comprising an unsaturated carboxylic acid or an alphaomegaaminecarboxylic acid.
When it comes to cross-linked polyolefins, by way of example of product (A), mention may be made of those containing ethylene and an unsaturated epoxide.
According to a first form of the invention, (A) is either a copolymer of ethylene and an unsaturated epoxide, or a polyolefins grafted by means of an unsaturated epoxide.
When it is a question of a polyolefin grafted by means of an unsaturated epoxide, it is understood by polyolefin, the polymers that comprise polyolefin motifs such as ethylene, propylene, butene-1, or any other alpha olefin motifs. By way of example, the following can be cited:
- polyethylenes such as LDPE, HDPE, LLDPE or VLDPE, polypropylene, ethylene / propylene copolymers, EPR (ethylene / propylene rubber) or even metallocene PE (copolymers obtained by monosite catalysis),
- styrene / ethylene-butene / styrene block copolymers (SEBS), styrene / butadiene / styrene block copolymers (SBS), styrene / isoprene / styrene block copolymers (SIS), styrene / ethylene block copolymers- propylene / styrene, ethylene / propylene / diene (EPDM).
- Copolymers of ethylene with at least one product chosen from the salts or esters of unsaturated carboxylic acids, or the vinyl esters of saturated carboxylic acids.
Advantageously, the polyolefin is chosen from LLDPE, VLDPE, polypropylene, ethylene / vinyl acetate copolymers or ethylene / alkyl (meth) acrylate copolymers. The density can advantageously be between 0.86 and 0.965, the melt index (MFI) can be between 0.3 and 40 (in g / 10 minutes 190 ° C with 2.16 kg).
When it comes to copolymers of ethylene and an unsaturated epoxide, mention may be made, for example, of the copolymers of ethylene of an alkyl (meth) acrylate and of an unsaturated epoxide or the copolymers of ethylene, of a vinyl ester of a saturated carboxylic acid and of an unsaturated epoxide. The amount of epoxide can be up to 15% by weight of the copolymer and the amount of ethylene at least 50% by weight.
Advantageously, (A) is an ethylene copolymer of an alkyl (meth) acrylate and an unsaturated epoxide.
Preferably, the alkyl (meth) acrylate is such that the alkyl has 2 to 10 carbon atoms.
The MFI (melt flow index) of (A) can be for example between 0.1 and 50 (g / 10 minutes at 190 ° C with 2.16 kg).
Examples of alkyl acrylate or methacrylate that can be used are especially methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate. Examples of unsaturated epoxides that can be used are especially:
- aliphatic glycidyl esters and ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate and itaconate, glycidyl acrylate and methacrylate, and
- alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5diglycidylcarboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endocis-bicyclo (2, 2, 1) -5 heptene-2,3-diglycidyl dicarboxylate.
According to another form of the invention, product (A) is a product that has two epoxide functions, such as, for example, the diglycidyl ether of bisphenol A (DGEBA).
As an example of product (B), mention may be made of those containing ethylene and an unsaturated carboxylic acid anhydride.
(B) is either a copolymer of ethylene and an unsaturated carboxylic acid anhydride, or a polyolefin grafted with an unsaturated carboxylic acid anhydride.
The polyolefin can be chosen from the polyolefins mentioned above and must be grafted with an unsaturated epoxide.
Examples of unsaturated dicarboxylic acid anhydrides that can be used as a constituent of (B) are especially maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride.
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By way of example, mention may be made of the copolymers of ethylene of an alkyl (meth) acrylate, of an unsaturated carboxylic acid anhydride and the copolymers of ethylene of a vinyl ester of saturated carboxylic acid and of an unsaturated carboxylic acid anhydride.
The amount of unsaturated carboxylic anhydride can be up to 15% by weight of the copolymer, and the amount of ethylene at least 50% by weight.
Advantageously, (B) is an ethylene copolymer of an alkyl (meth) acrylate and an unsaturated carboxylic anhydride. Preferably, the alkyl (meth) acrylate is such that the alkyl has 2 to 10 carbon atoms.
The alkyl (meth) acrylate can be chosen from those mentioned above.
The MFI of (B) can be for example between 0.1 and 50 (g / 10 minutes at 190 ° C with 2.16 kg).
According to another form of the invention, (B) can be chosen from aliphatic, alicyclic or aromatic polycarboxylic acids, and their partial or total anhydrides.
As examples of aliphatic acids, mention may be made of succinic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, adipic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, dodecenosuccinic acid and butane tetracarboxylic acid.
As examples of alicyclic acids, mention may be made of cyclopentane dicarboxylic acid, cyclopentanetricarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane dicarboxylic acid, hexane tricarboxylic acid, methylcyclopentane dicarboxylic acid, tetrahydrophthalic acid, tetrahydrophthalic acid, and methylenedomethylene-tetrahydrophthalic acid.
As examples of aromatic acids, mention may be made of phthalic acid, isophthalic acid, terephthalic acid, trimellilic acid, trimesic acid, pyromellitic acid.
By way of example of anhydrides, mention may be made of the partial or total anhydrides of these preceding acids.
Adipic acid is advantageously used.
We would not depart from the scope of the invention if a part of the copolymer (B) were replaced by an ethylene-acrylic acid copolymer or an ethylene-maleic anhydride copolymer, the maleic anhydride being totally or partially hydrolyzed. These copolymers can also comprise an alkyl (meth) acrylate, this part being able to represent up to 30% of (B).
When the product (C) comprises an unsaturated carboxylic acid, the fully or partially hydrolyzed products (B) may be mentioned by way of example. (C) is for example a copolymer of ethylene and an unsaturated carboxylic acid, and advantageously a copolymer of ethylene and (meth) acrylic acid.
Mention may still be made of the copolymers of ethylene, an alkyl (meth) acrylate and acrylic acid.
These copolymers have an MFI between 0.1 and 50 (g / 10 minutes at 190 ° C with 2.16 kg).
The amount of acid can be up to 10% by weight and preferably 0.5 to 5%. The amount of (meth) acrylate is 5 to 40% by weight.
(C) can also be chosen from alphaomegaaminecarboxylic acids, such as, for example, NH2- (CH2) s COOH, NH2- (CH2) -iüCOOH and NH2 (CH2) n-COOH and preferably aminoundecanoic acid.
The proportion of (A) and (B) necessary to form the cross-linked phase is determined according to the usual rules of the art, by the number of reactive functions present in (A) and (B).
For example, in the crosslinked phases containing (C) chosen from alphaomegaaminecarboxylic acids, if (A) is an ethylene copolymer of an alkyl (meth) acrylate and an unsaturated epoxide and (B) is an ethylene copolymer of an alkyl (meth) acrylate and an unsaturated carboxylic acid anhydride, the proportions are such that the ratio between the anhydride functions and the epoxide functions is close to 1.
The amount of alphaomegaaminecarboxylic acid is then 0.1 to 3% and preferably 0.5 to 1.5% of (A) and (B).
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If it is (C) comprising an unsaturated carboxylic acid, that is to say that (C) has been chosen, for example, from ethylene / alkyl (meth) acrylate / acrylic acid copolymers, The quantity of (C) and (B) can be chosen in such a way that the number of acid functions and anhydride functions is at least equal to the number of epoxide functions and the products (B) and (C) of so that (C) represents 20 to 80% by weight of (B) and is preferably 20 to 50%.
It would not go beyond the scope of the invention if a catalyst were added.
These catalysts are generally used for reactions between epoxy and anhydrides.
Among the compounds capable of accelerating the reaction between the epoxy function present in (A) and the anhydride or acid function present in (B), the following can be mentioned mainly:
- tertiary amines, such as dimethylaurylamine, dimethyl stearylamine, N-butylmorpholine, N, N-dimethylcyclohexylamine, benzyldimethylamine, pyridine, dimethylamino-4-pyridine, methyl-1-imidazole, tetramethylethylhydrazine, N, N-dimethylpiperazine, N, N, N ', N'-tetramethyl-1,6-hexanediamine, a mixture of tertiary amines with 16 to 18 carbons and known by the name of dimethylsulfamine
- 1,4-diaza bicyclo [2, 2, 2] octane (DABCO)
- tertiary phosphines, such as triphenylphosphine
- zinc alkyldithiocarbamates.
The amount of these catalysts is advantageously 0.1 to 3% and preferably 0.5 to 1% of (A) + (B) + (C).
When it comes to non-crosslinked polyolefins, mention can be made of the polyolefins described in the preceding paragraph and intended to be grafted with reactive groups. Products (A) or (B) or (C) of the preceding paragraph can still be cited but used alone so as not to cross-link. By way of example, mention may be made of the EPR, EPDM elastomers which can be grafted to facilitate their compatibilization with the copolyamide. Mention may still be made of acrylic elastomers, for example those of the NBR, hNbR, X-NBR type.
When it comes to the preparation of compositions (C), all conventional procedures for the synthesis of polyamides and copolyamides can be used.
The compositions according to the invention may further comprise at least one additive chosen from:
- colorants;
- pigments;
- brighteners;
- antioxidants;
- fire retardants;
- UV stabilizers;
- nucleating agents.
In one embodiment, the present invention also relates to structures comprising (described from the outermost layer of the object to the inner layer):
- an outer layer consisting of a composition (C),
- optionally a layer of aliphatic polyamide or of a mixture of aliphatic polyamide and polyolefins such as those described above,
- possibly a layer of binder,
- a central layer made up of a barrier material essentially chosen from among EVOH, fluorinated polymers, PPS, PBN, aliphatic polyketone, PA-MXD6, LCP, nanocomposite polymers and an alloy whose matrix is one of said materials,
- possibly a layer of binder,
- an inner layer, possibly conductive, made up of aliphatic polyamide or polyolefins or a compatibilized mixture of the two, as described above,
- optionally, a conductive layer of aliphatic polyamide or of a mixture of aliphatic polyamide and polyolefin as described above (this layer becomes the inner layer).
Binder is understood to mean any polymeric material capable of conferring on the structure the level of adhesion between layers required for the application. These binders are known per se. Examples include functionalized polyolefins, preferably grafted with maleic anhydride, or copolyamides or mixtures of copolyamides.
The composition of the layer consisting of aliphatic polyamide or polyolefin or a compatibilized mixture of the two is now described in greater detail.
ES 2 551 748 T3
Aliphatic polyamide refers to condensation products:
- of one or more amino acids, such as aminocaproic acids, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic, or of one or more lactams, such as caprolactam, oenantholactam and laurillactam;
- of one or more salts or mixtures of diamine, such as hexamethylenediamine, dodecamethylenediamine, with diacids, such as adipic, azelaic, suberic, sebacic and dodecanedicarboxylic acids.
Copolyamides can also be used advantageously. Mention may be made of the copolyamides resulting from the condensation of at least two alpha omega amino carboxylic acids or of two lactams or of one lactam and one alpha omega amino carboxylic acid. Mention may still be made of the copolyamides resulting from the condensation of at least one alpha omega aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.
PA 6 and PA 6-6 can be used.
The aliphatic polyamides can also be chosen from PA 11, PA 12, aliphatic polyamides resulting from the condensation of an aliphatic diamine with 6 to 12 carbon atoms and an aliphatic diacid with 9 to 12 carbon atoms, and copolyamides 11/12 either with more than 90% of motifs 11, or with more than 90% of motifs 12.
As an example of aliphatic polyamides resulting from the condensation of an aliphatic diamine with 6 to 12 carbon atoms and an aliphatic diacid with 9 to 12 carbon atoms, the following may be mentioned:
PA 6-12 resulting from the condensation of hexamethylene diamine and 1,12-dodecanedioic acid, PA 9-12 resulting from the condensation of diamine at carbon 9 and 1,12-dodecanedioic acid, PA 10- 10 resulting from the condensation of diamine at carbon 10 and 1,10-decanedioic acid, PA 10-12 resulting from the condensation of diamine at carbon 9 and 1,12-dodecanedioic acid.
As for the 11/12 copolyamides with more than 90% of motifs 11 or with more than 90% of motifs 12, they result from the condensation of amino 1-undecanoic acid with lauryllactam (or alpha omega amino acid in carbon 12).
Polyolefins have already been described above. Functionalized or non-functionalized polyolefins can be used.
When it comes to compatibilized blends of aliphatic polyamide and polyolefin, they are advantageously with a polyamide matrix.
According to a first preferred form of the mixture of polyamide and polyolefin, the polyolefin comprises (i) a high-density polyethylene (HDPE) and (ii) a mixture of a polyethylene and a polymer chosen from elastomers, polyethylenes of very high low density and ethylene copolymers, the mixture being co-grafted with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride.
According to a variant of this first form of the invention, the polyolefins comprise (i) a high density polyethylene (HDPE), (ii) a polymer chosen from elastomers, very low density polyethylenes and ethylene copolymers, this being polymer (ii) grafted with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, and optionally (iii) a polymer chosen from elastomers, very low density polyethylenes and ethylene copolymers.
According to a second preferred form of the mixture of polyamide and polyolefin, the polyolefin comprises (i) polypropylene and (ii) a polyolefin resulting from the reaction of a polyamide with a copolymer comprising propylene and an unsaturated monomer X, grafted or copolymerized .
According to a third preferred form of the mixture of polyamide and polyolefin, the polyolefin comprises (i) a polyethylene of the EVA, LDPE, VLDPE or metallocene type and (ii) a copolymer of ethylene - alkyl (meth) acrylate maleic anhydride.
According to a fourth preferred form of the mixture of polyamide and polyolefin, the polyolefin comprises two functionalized polymers which comprise at least 50 mol% of ethylene motifs and which can react to form a crosslinked phase.
When it comes to the first form, the proportions are advantageously the following (by weight):
ES 2 551 748 T3 of 50 to 75% polyamide, 5 to 15% co-grafted mixture, the complement being high-density polyethylene.
When it comes to the variant of the first form, the proportions are advantageously the following (by weight):
from 50 to 75% of polyamide, from 5 to 25% (advantageously from about 15 to 25%) of (ii) grafted, from 0 to 10% of (iii), the complement being polyethylene high density.
When it comes to the second form, the proportions are advantageously the following (by weight), the total being 100%:
50 to 75% polyamide, 20 to 30% polypropylene 3 to 10% of a polyolefin resulting from the reaction of a polyamide with a copolymer containing propylene and an unsaturated monomer X, grafted or copolymerized.
When it comes to the third form, the proportions are advantageously the following (by weight):
from 50 to 75% of polyamide, from 5 to 15% of an ethylene - alkyl (meth) acrylate - maleic anhydride copolymer, the complement being a polyethylene of the EVA, LLDPE, VLDPE or metallocene type.
When it comes to the fourth form, the proportions are advantageously the following (by weight):
40 to 95% polyamide, 60 to 5% of a mixture of an ethylene - alkyl (meth) acrylate - maleic anhydride copolymer and an ethylene - alkyl (meth) acrylate - glycidyl methacrylate copolymer .
[Examples]
Example 1: realization of a 11/10, T: 0.7 / 1.1 in moles
In a 100-liter reactor we load 12.2 kilos of terephthalic acid, 12.65 kilos of decanediamine, 10.15 kilos of amino 11 undecanoic acid, 10 liters of water, 175 g of stearic acid as a chain limiter, and 1.4 1000 g of siliconol as defoamer.
It is heated to 150 ° C and left for 2 hours at 5 bars. Then we heat up to 270 ° C, waiting long enough to reach 270 ° C at 20 bars.
It is kept up to atmospheric pressure in 2 hours and the poly is carried out in a stream of nitrogen for 45 minutes.
The inherent viscosity of metacresol is 1.27 dl / g. The MFI at 275 ° C and 2.16 kg is 3.0 g / 10 minutes. DSC (standard ISO 11357 20 ° C / minute) gives two melting peaks at 243 ° C and 259 ° C in the second heating. In dry DMA, the tangent delta is approximately 100 ° C.
Operative conditions:
• Device: RSA2 Voltage • Temperature: from -100 ° C to 300 ° C • Temperature rise: slope of 5 ° C per minute • Geometry: Voltage • Frequency: 10 rad / s • Conditioning: 1 night at 80 ° C / empty
<td>Composition</td><td></td><td>Mixing carried out on Werner® 30</td>
<td>PA 11/10, T</td><td></td><td> 99,4</td>
<td>P201 iodine, potassium iodide and copper iodide</td><td>Test tube type</td><td> 0,6</td>
<td>Tensile modulus</td><td>ISO 527</td><td>2020 MPa</td>
<td>Break at elongation</td><td>ISO 527</td><td> 150 %</td>
<td>Restriction threshold</td><td>ISO 527</td><td>60 MPa</td>
ES 2 551 748 T3
<td>Bending modulus</td><td>80 x 10 x 4</td><td>1790 MPa</td>
<td>Charpy AE Impact</td><td></td><td></td>
<td>Resilience + 23 ° C</td><td>80 x 10 x 4</td><td>10.4 ± 0.6 kJ / m<sup>2</sup></td>
<td>Resilience - 40 ° C</td><td>80 x 10 x 4</td><td>8.2 ± 0.6 kJ / m<sup>2</sup></td>
The absorption of water at saturation in water at 100 ° C for 8 days is 2.4%. The product resists the action of zinc chloride.
Example 2: realization of a 10. 10/10, T: 0.7 / 1.1 in moles
In a 100 liter reactor, we load 10.24 kilos of terephthalic acid, 18.05 kilos of decanediamine, 8.71 kilos of sebacic acid, 10 liters of water, 185 g of stearic acid as chain limiter and 1.5 g of siliconol 1000 as defoamer. It is heated to 150 ° C and left to stand for 2 hours at 4.5 bars. Next, we heat up to 280 ° C waiting long enough to reach 280 ° C at 20 bars. It is expected to reach atmospheric pressure in 2 hours and the poly is carried out in a stream of nitrogen in 60 minutes.
The inherent viscosity of metacresol is 1.25 dl / g. The MFI at 275 ° C with 2.16 kilos is 5g / 10 minutes.
DSC gives two melting peaks at 240 and 255 ° C.
The tangent delta in dry DMA on 80 x 10 x 4 bars is 85 ° C.
Example 3: improvement of thermal resistance: measured by life by loss of elongation at 50% relative
<td>Stabilization to 0.6% iodine 201 by WERNER 30 compound</td><td>Elongation at break in% IFC</td><td>Elongation at break after 48 hours at 140 ° C</td><td>relative%</td><td>Elongation at break after 2016 hours at 140 ° C</td><td>relative%</td>
<td>1110, T</td><td> 175</td><td> 25</td><td> 14</td><td>nm *</td><td>nm</td>
<td>11/10, T + 13% BBSA (plasticizer)</td><td> 240</td><td> 25</td><td> 10</td><td>nm</td><td>nm</td>
<td>11/10, T + 13% cocktail LT **</td><td> 140</td><td> 25</td><td> 18</td><td>nm</td><td>nm</td>
<td>11/10, T + 13% BBSA + 13% cocktail LT **</td><td> 180</td><td> 60</td><td> 33</td><td>nm</td><td>nm</td>
<td>11/10, T + 30% PA11</td><td> 147</td><td> 95</td><td> 65</td><td> 129</td><td> 88</td>
<td colspan="6">nm * = not measured since the relative% is less than 50% cocktail LT **: lotader 4700 (50%) + lotader AX 8900 (25%) + lucaléne 3110 (25%) Lotader AX 8900 is a glycidyl ethylene methacrylate copolymer with 8% GMA and FMI 5 (190 ° C2.16kg) Lotader 4700 is an ethylene-ethyl acrylate-MAH copolymer with 30% acrylate and 12% MAH. Lucaléne 3110 = ethylene / butyl acrylate / acrylic acid copolymer of composition by weight 88/8/4 (BASF)</td>
Example 4: improvement of thermal resistance: test on tubes after 72 hours at 150 ° C and an impact at 40 ° C
<td>PA 11/10, T</td><td></td><td> 86,4</td><td> 86,4</td><td> 73,4</td><td> 68,5</td><td> 68,5</td>
<td>BBSA</td><td></td><td> 13</td><td></td><td> 13</td><td> 4</td><td> 5</td>
<td>lotader 4700</td><td></td><td></td><td> 6,5</td><td> 6,5</td><td> 8</td><td> 5</td>
<td>lotader ax8900</td><td></td><td></td><td> 3,25</td><td> 3,25</td><td> 4</td><td> 2,5</td>
<td>Lucalene 3110</td><td></td><td></td><td> 3,25</td><td> 3,25</td><td> 4</td><td> 2,5</td>
<td>Anti 6</td><td></td><td> 0,6</td><td> 0,6</td><td> 0,6</td><td> 0,6</td><td> 0,6</td>
<td>PA11</td><td></td><td></td><td></td><td></td><td> 10</td><td> 15</td>
ES 2 551 748 T3
<td>MM black euthylen 6005-c4</td><td></td><td></td><td></td><td></td><td> 0,9</td><td> 0,9</td>
<td></td><td>Test tube type</td><td></td><td></td><td></td><td></td><td></td>
<td>Bending modulus MPA</td><td>80 x 10 x 4</td><td> 1020</td><td> 1430</td><td> 580</td><td>1250 MPa</td><td>1270 MPa</td>
<td>Charpy impact AE</td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>Resilience + 23 ° C kj / m<sup>2</sup></td><td>80 x 10x 4</td><td> 11.9 ± 1,2</td><td> 23,4 ± 2,1</td><td> 107 ± 1</td><td> 59,9 ± 4</td><td> 20,1 ± 1,5</td>
<td>Resilience -40 ° C kj / m<sup>2</sup></td><td>80 x 10x 4</td><td> 3,3 ± 0,3</td><td> 12,0 ± 1,7</td><td> 5,3 ± 0,2</td><td> 9,5 ± 1,3</td><td> 8,3 ± 0,3</td>
<td>Impact at -60 ° C on tubes after 72 h00 at 150 ° C</td><td>6 x 8 tube</td><td>BREAK</td><td>BREAK</td><td>BREAK</td><td>DOES NOT BREAK</td><td>DOES NOT BREAK</td>
<td>Impact at -50 ° C on tubes after 192 h00 to 150 ° C</td><td>6 x8 tube</td><td>BREAK</td><td>BREAK</td><td>BREAK</td><td>DOES NOT BREAK</td><td>DOES NOT BREAK</td>
<td>Impact at -40 ° C on tubes after 72 h00 at 160 ° C</td><td>6 x8 tube</td><td>BREAK</td><td>BREAK</td><td>BREAK</td><td>DOES NOT BREAK</td><td>DOES NOT BREAK</td>
Resume
Structure comprising flexible semi-aromatic polyamides with weak moisture absorption
The present invention refers to a structure comprising at least one layer made up of a composition (C) and other layers made up of other materials, the composition (C) comprising, by weight, the total being 100:
- from 60 to 99.5% of at least one copolyamide of formula X / Y, Ar, in which:
- Y represents the remains of an aliphatic diamine with 8 to 20 carbon atoms,
- Ar represents the residues of an aromatic carboxylic diacid,
- X represents either the residues of the aminoundecanoic acid NH2- (CH2) 10-COOH, of the lactam 12 or of the corresponding amino acid, or the motif of Y, x residue of the condensation of diamine with an aliphatic diacid (x) from 8 to 20 carbon atoms, or else the Y motif, I remainder of the condensation of the diamine with isophthalic acid,
- from 0.5 to 40% of at least one product chosen from plasticizers, nano-fillers, polyolefins, cross-linked polyolefins and additives.
Contents10
24 members in 10 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 0309641 | France | A | |
| 0309641 | France | – | |
| 0400906 | France | A | |
| 0400906 | France | – |
Members24
| Document | Office | Kind | |
|---|---|---|---|
| CA2478747A1 | Canada | A1 | |
| EP1505099A2 | European Patent Office (EPO) | A2 | |
| FR2858625A1 | France | A1 | |
| FR2858626A1 | France | A1 | |
| KR20050016144A | Republic of Korea | A | |
| JP2005054191A | Japan | A | |
| CN1590461A | China | A | |
| US2005096430A1 | United States of America | A1 | |
| BRPI0403150A | Brazil | A | |
| FR2858625B1 | France | B1 | |
| FR2858626B1 | France | B1 | |
| RU2004123917A | Russian Federation | A | |
| RU2273651C1 | Russian Federation | C1 | |
| EP1505099A3 | European Patent Office (EPO) | A3 | |
| KR100744432B1 | Republic of Korea | B1 | |
| US7388048B2 | United States of America | B2 | |
| US2008249238A1 | United States of America | A1 | |
| US7625972B2 | United States of America | B2 | |
| CN100572451C | China | C | |
| EP2264083A1 | European Patent Office (EPO) | A1 | |
| EP2264083B1 | European Patent Office (EPO) | B1 | |
| ES2551748T3This record | Spain | T3 | |
| EP1505099B1 | European Patent Office (EPO) | B1 | |
| BRPI0403150B1 | Brazil | B1 |
Numbers
- Publication
- 2551748
- Application
- 10173235
Titles2
- Spanish
- Estructura que comprende poliamidas semiaromáticas flexibles con una débil absorción de humedad
- English
- Structure comprising flexible semi-aromatic polyamides with weak moisture absorption
Classification
- CPC, 13
- B32B27/34
- C08G69/12
- C08G69/36
- C08L23/02
- C08L51/06
- C08L77/00
- C08L77/06
- H01B3/305
- C08L77/10
- C08G73/02
- B82Y30/00
- B32B27/08
- B32B27/32
- IPC, 13
- C08G69 36
- C08L77 00
- B32B27 34
- H01B3 38
- C08G69 12
- B32B1 00
- C08G69 02
- C08G73 02
- C08L23 02
- C08L51 06
- C08L77 06
- C08L77 10
- H01B3 30