EP1456300A1 - Composition thermoplastique comprenant un additif polymere hyperbranche, articles realises a partir de ce materiau - Google Patents
Composition thermoplastique comprenant un additif polymere hyperbranche, articles realises a partir de ce materiauInfo
- Publication number
- EP1456300A1 EP1456300A1 EP02801134A EP02801134A EP1456300A1 EP 1456300 A1 EP1456300 A1 EP 1456300A1 EP 02801134 A EP02801134 A EP 02801134A EP 02801134 A EP02801134 A EP 02801134A EP 1456300 A1 EP1456300 A1 EP 1456300A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- composition according
- hyperbranched
- matrix
- copolyamide
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/005—Dendritic macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S424/00—Drug, bio-affecting and body treating compositions
- Y10S424/16—Dendrimers and dendritic polymers
Definitions
- thermoplastic compositions comprising a thermoplastic polyamide matrix and at least one additive which modifies the interaction of the matrix with an agent.
- polymer denotes both a homopolymer and a copolymer.
- Thermopiastic polyamides are raw materials capable of being transformed by molding, injection molding, injection blow molding, extrusion, extrusion / blow molding or spinning, in particular into multiple articles such as parts (for example for bodywork) blown, extruded, or molded, yarns, fibers or films.
- the external agent that is water and internal agents which can be incorporated into the matrix in order to give it a certain number of properties.
- antistatic agents for example, antistatic agents, adhesives, flame retardants, odoriferous substances, flame retardants, antioxidants, heat or UV stabilizers, dyes, or impact resistance modifiers.
- thermoplastic copolyamides in particular for the transformation into textile threads: better absorption of water therefore better feel of the threads (comparable to that of cotton), better wearing comfort, improvement of fixing dyes, etc.
- copolyamides more particularly targeted by the invention are linear copolyamides of the type of those obtained from diacids and diamines. Such as polyamide 6.6.
- These hyperbranched polyamides can be functionalized by involving in chain copolycondensation, a chain-stopping monomer type R "'- A. They have a size between a few nanometers and several tens of nanometers.
- one of the essential objectives of the present invention is to provide an additive which modifies the interaction, with respect to at least one agent, of a thermoplastic copolyamide matrix of the type of copolyamides obtained by polycondensation of diacids and diamines, said additive having to be:
- thermoplastic copolyamide - able to allow the controlled modification of the interaction of the thermoplastic copolyamide, with respect to an internal or external chemical agent (for example water: hydrophilicity / hydrophobicity).
- an internal or external chemical agent for example water: hydrophilicity / hydrophobicity
- thermoplastic polymer composition comprising a thermoplastic polyamide matrix and at least one additive chosen from modifiers of the interaction of the thermoplastic copolyamide, with respect to an internal or external agent (for example water: hydrophilicity / hydrophobia), so that it can be easily and economically adapted to multiple applications, especially textiles, while being able to be shaped in the molten state: injection molding, injection / blowing, extrusion / blowing, filming, extrusion, spinning.
- an internal or external agent for example water: hydrophilicity / hydrophobia
- Another essential objective of the invention is to provide articles obtained by transformation (molding, injection molding, injection / blowing, extrusion / blowing, extrusion or spinning) of the composition as defined in the objectives above.
- thermoplastic composition comprising: a thermoplastic copolyamide matrix of the type of copolyamides obtained by polycondensation of diacids and diamines; ⁇ and at least one additive modifying the interaction of the matrix, with respect to at least one agent, this additive consisting of at least one polymer:
- R 2 being a substituted or unsubstituted hydrocarbon radical, of the silicone, linear or branched alkyl, aromatic, arylalkyl, alkylaryl or cycloaliphatic radical which may comprise one or more unsaturations and / or one or more heteroatoms. characterized in that the matrix and the functionalized hyperbranched polymer additive are not compatible.
- hyperbranched polymer is meant a branched polymer structure obtained by polymerization in the presence of compounds having a functionality greater than 2, and the structure of which is not perfectly controlled. They are often statistical copolymers.
- the hyperbranched polymers can, for example, be obtained by reaction between, in particular, multifunctional monomers, for example trifunctional and bifunctional, each of the monomers carrying at least two different reactive polymerization functions.
- the hyperbranched polymer of the invention is chosen from polyesters, polyesteramides and hyperbranched polyamides.
- the hyperbranched polymer additive of the invention is preferably a hyperbranched polyamide of the type of those obtained by reaction between:
- AR-Bf in which A is a reactive polymerization function of a first type, B is a reactive polymerization function of a second type and capable of reacting with A, R is a hydrocarbon entity optionally comprising heteroatoms, and f is the total number of reactive functions B per monomer: f> 2, preferably 2 ⁇ f ⁇ 10;
- R 1 is a substituted or unsubstituted hydrocarbon radical, of the silicone, linear or branched alkyl, aromatic, alkylaryl, arylalkyl or cycloaliphatic type which may comprise unsaturations and / or heteroatoms;
- - n 1, preferably 1 ⁇ n ⁇ 100;
- R 2 is non-reactive with the matrix, so that the functionalized hyperbranched polymer does not affect the structural integrity of the matrix with which it is mixed.
- the functionalized hyperbranched polymer advantageously results in only a small variation in the molar mass of the matrix, compared with a control composition comprising the same matrix not additivated by hyperbranched polymer. Any possible reduction in the molar mass of the matrix is preferably limited to less than 7% relative to the control composition.
- the molar mass is defined as the maximum of the distribution of the molar masses of the matrix, in Polystyrene equivalent, by Gel Permeation Chromatography (GPC), with detection by refractometry.
- GPC Gel Permeation Chromatography
- the molar mass measurement is carried out on the composition to be analyzed and on the control composition, extruded, solidified, put in the form of granules, according to protocol P given in detail below.
- the functionalized hyperbranched polymer additive is not compatible with the matrix, so that the thermoplastic matrix (for example PA 6.6) and the hyperbranched polymer, while being dispersible in one another , are subject to a phenomenon of demixing, which does not however prevent not adjusting the behavior of the material vis-à-vis a chemical or physical agent, internal or external (for example water) by playing qualitatively and quantitatively on the non-compatible incorporated PAHB incorporated.
- the thermoplastic matrix for example PA 6.6
- the hyperbranched polymer while being dispersible in one another , are subject to a phenomenon of demixing, which does not however prevent not adjusting the behavior of the material vis-à-vis a chemical or physical agent, internal or external (for example water) by playing qualitatively and quantitatively on the non-compatible incorporated PAHB incorporated.
- non-compatible functionalized hyperbranched polymer matrix and additive is meant that the mixture of these two elements of the composition forms two distinct phases.
- a first mode of characterization of the non-compatibility of the hyperbranched polymer with respect to the matrix is the observation of the two phases in scanning or transmission electron microscopy and / or in atomic force microscopy.
- composition according to the invention is advantageously characterized in that the two phases can be observable by transmission electron microscopy (with a magnification for example greater than or equal to 2000) optionally with the use of a marker such as Os0 or Ru0.
- the maximum (s) of this curve corresponds (s) to the glass transition temperature (s) (Tg) of the material tested .
- miscibility between two polymers can be evaluated by studying their glass transition by a dynamic mechanical analysis technique: ⁇ if the polymers are compatible (miscible), we will observe a single glass transition, generally intermediate between that of the two components ; a if the polymers are not compatible, two glass transitions will be observed, very close to those of each of the components. If one of the components is present in small quantities (less than 10%), its glass transition may not be detected.
- composition according to the invention is advantageously characterized by a glass transition temperature measured by mechanical dynamic analysis, substantially identical to that of the matrix, preferably identical to within 0.1 ° C.
- the functionalized hyperbranched polymer additive is present, in the composition of the invention, in particular in the form of size nodules advantageously between 1 and 500 nm, for example of the order of 100 to
- non-compatible functionalized hyperbranched polymer nodules are dispersed in the copolyamide matrix and can even be repelled and concentrated on the surface of the article, for example a wire, obtained from the composition comprising the matrix and the hyperbranched polymer.
- the non-compatible functionalized hyperbranched polymer additive is easy to use and economical.
- the hyperbranched copolymer constituting the functionalized hyperbranched polymer additive has a content of acid or amino terminal groups (GT) (expressed in meq / kg) less than or equal to 50, preferably less than or equal to 20, and more preferably still less than or equal to 10.
- GT acid or amino terminal groups
- the composition according to the invention is free of hyperbranched polymer additives resulting in a reduction in the molar mass of the matrix M greater than or equal to 7% compared to a control composition comprising the same matrix M not additivated by hyperbranched polymer , the molar mass measurement being carried out according to a determined protocol P.
- the molar mass measurement protocol P is given below.
- the molar mass is defined as the maximum of the distribution of the molar masses of the matrix, in polystyrene equivalent, by gel permeation chromatography (G PC), in detection by refractometry, as defined in the protocol. P given in the examples below.
- the abovementioned protocol P for measuring the molar mass of the matrix M in a composition to be analyzed and in a control composition involves an extrusion, which leads to the production of rods.
- the rods (previously put in the form of granules) are then subjected to the determination of molar mass proper.
- extrusion constitutes one of the means for mixing in the molten state of the constituents M and hyperbranched functionalized polymer.
- the molar mass measurement is carried out on the composition to be analyzed and on the control composition which is extruded, solidified and put in the form of granules.
- the protocol P for measuring the molar mass of the compositions according to the invention and of the control compositions is as follows:
- the mixture is introduced into a twin-screw extruder.
- This mixture is melted in the extruder at a temperature Q> Qf US ion of the matrix M + 30 ° C.
- the homogenization of M / hyperbranched polymer is thus carried out for 5 min and rods are collected at the extruder outlet, then put in the form of granules.
- the actual molar mass measurement is carried out on the granules by gel permeation chromatography (GPC) in dichloromethane after derivatization of the polyamide by trifluoroacetic anhydride, compared to polystyrene standards.
- the detection technique used is refractometry. 2 / Emo compositions
- a molar mass measurement of the same matrix M is carried out on a composition comprising the matrix M without hyperbranched polymer additive.
- the method is carried out on granules of copolyamide M obtained in the same way as that indicated in point 1 above, with the difference that the granules do not contain a hyperbranched polymer additive.
- the functionalized hyperbranched polyamide additive of the composition is characterized in that: the hydrocarbon-based entities R, R ′ of the monomers (I) and (11) respectively, each comprise: at least one aliphatic radical linear or branched; and / or at least one cycloaliphatic radical; and / or at least one aromatic radical comprising one or more aromatic rings; iv. and / or at least one arylaliphatic radical; these radicals (i), (ii), (iii), (iv) possibly being substituted and / or comprising heteroatoms;
- A, A ' is a reactive function of the amino type, amine salt or of the acid, ester, acid halide or amide type;
- B, B ' is a reactive function of the acid, ester, acid halide or amide type or of the amino type, amine salt.
- the reactive polymerization functions A, B, A ', B' more especially retained are those belonging to the group comprising the carboxylic and amino functions.
- carboxylic function is meant within the meaning of the invention, any COOH acid function or derivative of the ester, acid halide (chloride), anhydride, or amide type.
- the non-compatible functionalized hyperbranched polyamide can consist of a mixture of several different monomers (I), of several different monomers (II), and / or of several monomers (IV) of different functionalization.
- the bifunctional monomers (II) are spacers in the three-dimensional structure.
- the functional spacer monomers (III), the chain-limiting monomers (IV), and / or the "core" type monomers (III) can be in the form of prepolymers.
- the functionalized hyperbranched polyamide additive comprises monomers (III) according to a molar ratio III / L + II + IV which is defined as follows: III / I + II + IV ⁇ 1/150 and preferably III / l + ll + IV ⁇ 1/100
- a first group of large hyperbranched polyamide can be isolated, in which:
- the monomer (I) is chosen from the group comprising: - 5-amino-isophthalic acid,
- the bifunctional monomer of formula (II) is chosen from the group comprising:
- the alkyl radical R 2 for functionalizing the hyperbranched polymer is chosen from: linear alkyls comprising from 8 to 30 carbon atoms, preferably from 10 to 20 carbon atoms, ⁇ polyetheralkylenes, preferably polyethylene and / or propylene glycol,
- Examples of monomers (IV) of functionalization there may be mentioned n-hexadecylamine, n-octadecylamine, or alternatively poly (oxyethylene-co-oxypropylene (Jeffamine ® M 1000).
- 0.01 to 50 preferably 0.1 to 20 and more preferably still 0.5 to 10.
- the radicals R 2 for functionalization of the hyperbranched polymer are of the same type throughout the hyperbranched polymer.
- the hyperbranched polymer may comprise radicals R 2 of the alkyl type only, and not a mixture of several types of radicals R 2 .
- AR-Bf in which A is a reactive polymerization function of a first type, B is a reactive polymerization function of a second type and capable of reacting with A, R is a hydrocarbon entity optionally comprising heteroatoms, and f is the total number of reactive functions B per monomer: f> 2, preferably 2 ⁇ f ⁇ 10; - optionally at least one bifunctional monomer of formula (II) below:
- R 1 is a substituted or unsubstituted hydrocarbon radical, of the silicone, linear or branched alkyl, aromatic, alkylaryl, arylalkyl or cycloaliphatic type which may comprise unsaturations and / or heteroatoms;
- R 2 is a radical chosen from hydrocarbon radicals, substituted or unsubstituted, of the genus silicone, linear or branched alkyl, aromatic, arylalkyl, alkylaryl or cycloaliphatic which can comprise one or more unsaturations and / or one or more heteroatoms, and
- a "is a reactive function of the same nature as A or A ′ is carried out by polycondensation in the molten phase between monomers (I), optionally monomers (11), which also react with each other and with monomers (IV), and optionally with monomers (III).
- Copolycondensation polymerization is carried out, for example, under conditions and according to a procedure equivalent to those used for the manufacture of linear polyamides, for example from monomers (II).
- thermoplastic copolyamide matrix As regards the essential constituent quantitatively of the composition according to the invention, namely the thermoplastic copolyamide matrix, it is selected from the group comprising: Nylon 6.6, Nylon 9.9, polyamides 4-6, 6-10, 6-12, 6-36, 12-12, their copolymers and mixtures.
- the polyphthalamides obtained from terephthalic and / or isophthalic acid such as the polyamide sold under the trade name AMODEL, the copolyamides obtained from adipic acid, from hexamethylene diamine and caprolactam.
- thermoplastic (co) polymer (s) is (are) a polyamide 6.6.
- the polymer matrix M of the composition consists of a mixture and / or alloy of a polyamide with one or more other polymers, preferably polyamides or copolyamides.
- a mixture and / or alloy of (co) polyamide with at least one polymer of the propylene polyoxide (PPO), polyvinyl chloride (PVC), polyacrylobutadiene-styrene (ABS) type is also conceivable.
- At least one reinforcing and / or filling filler chosen from the group comprising fibrous fillers such as glass fibers, mineral fillers such as clays, kaolin, reinforcing nanoparticles or in thermosetting material, and powdered fillers such as talc.
- the rate of incorporation in reinforcing filler conforms to standards in the field of composite materials. It may for example be a charge rate of 1 to 90%, preferably 10 to 60%, and more specifically 50%.
- hyperbranched polymer additives can also be combined with other additives such as impact modifiers such as optionally grafted elastomers.
- composition according to the invention can also contain any other suitable additives or adjuvants, for example fillers (Si0 2 ), flame retardants, UV stabilizers, heat stabilizers, matifiers (Ti0 2 ), lubricants , plasticizers, compounds useful for the catalysis of the synthesis of the polymer matrix, antioxidants, antistatics, pigments, dyes, molding aid additives or surfactants.
- suitable additives or adjuvants for example fillers (Si0 2 ), flame retardants, UV stabilizers, heat stabilizers, matifiers (Ti0 2 ), lubricants , plasticizers, compounds useful for the catalysis of the synthesis of the polymer matrix, antioxidants, antistatics, pigments, dyes, molding aid additives or surfactants. This list is in no way limiting.
- compositions according to the invention can be used as a raw material in the field of engineering plastics, for example for the production of injection molded or injection / blow molding articles, extrusion by conventional extrusion or by extrusion blow molding, or films.
- compositions according to the invention can also be formed into threads, fibers, filaments by melt spinning.
- the functionalized hyperbranched polymer additive is easily dispersible in the thermoplastic polyamide polymer matrix.
- a first method could consist in mixing the functionalized hyperbranched polymer in molten resin, and possibly subjecting the mixture to significant shearing, for example in a twin-screw extrusion device, in order to achieve good dispersion.
- a twin-screw extrusion device is generally arranged upstream of the means for shaping the molten plastic material (molding, extrusion, spinning).
- this mixture is extruded in the form of rods which are then cut into granules.
- the molded parts are then produced by melting the granules produced above and feeding the composition in the molten state in suitable molding, injection, extrusion or spinning devices.
- the composition obtained at the extruder outlet optionally directly feeds a spinning installation.
- a second method may be that which consists in mixing the hyperbranched polymer with the monomers, in the polymerization medium of the thermoplastic matrix or during the polymerization.
- molten matrix resin a concentrated mixture of a resin and functionalized hyperbranched polymer, prepared for example according to one of the methods described above.
- the present invention relates to the articles obtained by shaping, preferably, by molding, injection molding, injection / blow molding, extrusion, extrusion / blow molding or spinning, of one of the polymer compositions with polymer additives hyper connected and as defined above.
- These articles can be yarns, fibers, films, or filaments.
- composition according to the invention may also be articles molded from the composition according to the invention comprising polyamide, hyperbranched polymer as defined above, and optionally reinforcing fibers (glass).
- the hyperbranched polymer additive modifies the interaction of the article matrix with an agent, on the surface of the article and / or in the mass (volume) of the article.
- the agent whose interaction with the copolyamide matrix is modified by the functionalized hyperbranched polymer is water.
- a subject of the invention is also the use as an additive modifying the interaction, with respect to at least one agent, of a thermoplastic copolyamide matrix based on: o at least one linear copolyamide of the type of those obtained from diacids and diamines; o and at least one hyper-branched polymer, functionalized as defined above.
- FIG. 1 is a circuit diagram of the inhibition test according to Example 7.
- Figure 2b is identical to Figure 2a at a time t> 0.
- FIG. 3 is an observation photograph of a transmission electron microscope view (magnification x 5000) of a wire made of a material made by extrusion as described in Example 6, from PA66 loaded at height 5% by weight with PAHB according to Example 1.
- the monomers are fully loaded at the start of the test in the reactor at 20 ° C. 190.4 g of solid hexadecylamine with 90% purity (0.71 mol), 100.4 g of ⁇ -caprolactam (0.89 mol), 80.4 g of acid are successively introduced into the reactor. -aminoisophthalic (0.44 mol), 18.6 g of acid 1, 3.5- benzene tricarboxylic (0.09 mol) and 0.76 g of a 50% aqueous solution (w / w) of hypophosphorous acid. The reactor is purged by a succession of 3 sequences of evacuation and restoration of atmospheric pressure using dry nitrogen.
- the reaction mass is gradually heated from 20 to 260 ° C with stirring, in about 200 min.
- the reactor After 63 minutes with stirring at 260 ° C, the reactor is put under progressive vacuum over 61 min. The minimum vacuum reached is 1 to 2 mBar and is then maintained for an additional 30 min. About 8ml of distillate are collected.
- the stirring is stopped and the reactor is placed under nitrogen overpressure.
- the bottom valve is gradually opened and the polymer is poured into a stainless steel beaker.
- the product is then cooled in the dry ice under a stream of nitrogen. 339 g of polymer are collected, including the samples being synthesized.
- the hyperbranched copolyamide obtained is vitreous.
- the reaction is carried out at atmospheric pressure in a 0.5 I glass reactor commonly used in the laboratory for the melt phase synthesis of polyesters or polyamides.
- the reaction mass is gradually heated from 90 to 260 ° C with stirring, in about 200 min.
- the temperature is maintained at 260 ° C. with stirring for 60 minutes.
- the reactor is then placed under progressive vacuum over 38 min.
- the minimum vacuum reached is 5 mBar and is then maintained for an additional 65 min. 12.5 g of distillate are collected.
- the polymer is cooled in the reactor under a stream of nitrogen. 157.9 g of polymer are collected (without taking into account the samples in progress).
- the hyperbranched copolyamide is vitreous and can easily be crushed into flakes or ground.
- the reaction is carried out at atmospheric pressure in a 1.0 I autoclave commonly used for the synthesis in the melt phase of polyesters or polyamides.
- the monomers are completely loaded at the start of the test into the reactor at room temperature. 60.2 g of ⁇ -caprolactam (0.532 mol), 96.4 g of 5-aminoisophthalic acid (0.532 mol), 4.5 g of 1,3,5-benzene tricarboxylic acid are successively introduced into the reactor. 0.021 mol) 160.0 g of hexadecylamine at 90% purity (0.596 mol), and 0.380 g of a 50% aqueous solution (w / w) of hypophosphorous acid. The reactor is purged by a succession of 3 sequences of evacuation and restoration of atmospheric pressure using dry nitrogen.
- the reaction mass is gradually heated to a temperature of 260 ° C with stirring, in about 200 min.
- the reactor After 40 minutes at 260 ° C. with stirring, the reactor is put under progressive vacuum over 60 min. The minimum vacuum is then maintained for an additional 30 min (less than 1 mBar). 13.5 g of distillate are recovered. At the end of the cycle, the stirring is stopped and the reactor is placed under nitrogen overpressure. The bottom valve is then gradually opened and the polymer is poured at 260 ° C into a stainless steel bucket. The product is then cooled in the dry ice under a stream of nitrogen. 265.0 g of polymer are collected.
- the hyperbranched copolyamide obtained is vitreous and can easily be crushed into flakes or ground.
- the reaction is carried out at atmospheric pressure in a 7.5 I autoclave commonly used for the synthesis in the melt phase of polyesters or polyamides.
- the monomers are fully loaded at the start of the test into the reactor preheated to 70 ° C. and with stirring at 80 rpm. Successively introduced into the reactor 1408.9 g of hexadecylamine fused to 90% purity (5.25 mol), 1033.5 g of ⁇ -caprolactam (9.13 mol), 827.2 g of acid 5 - aminoisophthalic (4.57 mol), 48 g of 1,3,5-benzene tricarboxylic acid (0.23 mol) and 6.5 g of a 50% aqueous solution (w / w) of hypophosphorous acid .
- the reaction mass is gradually heated from 70 to 260 ° C with stirring, in about 200 min.
- the polymer is poured into a stainless steel beaker, then cooled in dry ice under a stream of nitrogen. 2837.5 g of polymer are collected.
- the hyperbranched copolyamide obtained is vitreous.
- the respective overall composition is 1/7/1 molar in AIPA / CL / PEG, equivalent approximately to 50/50% by mass of hyperbranched polyamide / Jeffamine ®
- the reaction is carried out at atmospheric pressure in a 1 I autoclave commonly used for the synthesis in the melt phase of polyesters or polyamides.
- the reaction mass is gradually heated to a temperature of 220 ° C. with stirring, in approximately 200 min.
- Jeffamine M 1000 ® is a polyamine (oxyethylene-co-oxypropylene) monoamine diblock, of respective DP 19 and 3, supplied by Huntsman ® .
- the temperature of the reaction mass is then brought to 260 ° C. in 40 min, then left in a tray for 1 hour.
- the reactor is then placed under maximum vacuum, gradually over a period of one hour, then maintained under these conditions for an additional 30 min.
- the stirring is stopped and the reactor is then brought back to atmospheric pressure under nitrogen, then under an overpressure of 5 Bar.
- the bottom valve is gradually opened and the polymer is poured at 260 ° C in an Erlenmeyer flask.
- the product is then cooled in the dry ice under a stream of nitrogen. 635 g of polymer are collected.
- the hyperbranched copolyamide obtained is in the form of a hard wax at room temperature. Differential thermal analysis shows two melting peaks, at 28 and 204 ° C. A glass transition is also observed at 155 ° C.
- Example 6 Preparation of the samples of polyamide 6.6 yarns containing non-compatible functionalized PAHBs according to Examples 1 to 4 and measurement of the molar masses of the matrix M of the functionalized M / PAHB compositions of Examples 1 and 2, measured on the yarns.
- the polyamide 66 used is a Polyamide 66 not comprising titanium dioxide, with a relative viscosity of 2.5 (measured at a concentration of 10 g / l in 96% sulfuric acid).
- PAHB 2% and 5% by weight relative to the total weight of the composition
- the incorporation of PAHB (2% and 5% by weight relative to the total weight of the composition) in PA66 is done by mixing powders and then in the melt phase using a twin screw extrusion device. The molten mixture is then spun with a speed at the first call point of 800 m / min, so as to obtain a continuous multifilament yarn of 90 dtex for 10 filaments.
- the multifilament or wire consists of 10 strands (the die consists of 10 holes) and the diameter of one strand is approximately 30 ⁇ m.
- Example 7 Characterization of the behavior with respect to water of the samples of functionalized polyamide 6.6 / PAHB yarns obtained in Example 6
- This characterization is carried out by capillary soaking of water in the multifilament consisting of 10 strands. Between the strands (typically three strands) a non-cylindrical capillary forms in which the water will rise with a contact angle ⁇ between the water and the strand.
- This angle ⁇ is characteristic of the hydrophilicity / hydrophobicity of the surface of the wire.
- the principle of the measurement is as follows: the penetration of a liquid within a capillary network is governed by a competition between the capillary forces and the force of gravity.
- the capillary network is here formed between the strands of the multifilament, it is not a cylindrical model network but it can be modeled as an assembly of cylindrical capillaries having an equivalent radius R.
- R radius of the capillary (m) ⁇ : viscosity of the liquid (Pa.s) ⁇ : surface tension of the liquid (N / m) ⁇ : contact angle between the liquid and the solid.
- the assembly used to visualize the imbibition and shown in Figure 1 attached is as follows: the test thread formed by a multifilament is tensioned using a pulley system and two 20g masses hung on each end of the wire. The wire is immersed in a solution of colored water in order to visualize the imbibition.
- the dye chosen, which does not interact with the polyamide, is methylene blue at a concentration of 0.2%.
- the capillary rise is filmed by a camera connected to a video recorder and to a screen with a stopwatch. The zero of the experiment corresponds to the moment when the wire is immersed in the colored solution ( Figures 2a and 2b).
- Example 8 Preparation of Samples of Hydrophilic Polyamide 6.6 Yarns Added with Functionalized PAHB Not Compatible According to Example 5
- Polyamide 66 comprising 0.3% by weight of titanium dioxide, with a relative viscosity of 41 (measured at 8.4% of polymer in 90% formic acid). * Hydrophilic PAHB from Example 5.
- Granules comprising the polyamide and one of the additives are prepared by extrusion in a twin screw extruder with supply of granules of each of the constituents.
- the compositions thus produced are given in Table 9. Table 9
- Wire is melted from the granules prepared at a temperature of 285 ° C.
- the yarn is wound at a speed of 4200 m / min and at a titer of 45 dtex for 10 filaments.
- the filaments from several spools are woven so as to form socks 5 cm in diameter.
- the moisture uptake of the compositions is measured by variation in weight after a residence time of 48 hours in an enclosure conditioned at a relative humidity of 94% at 30 ° C or 54% at 30 ° C, then a passage of 16h in oven regulated at 80 ° C under a pressure of 7 mm of mercury.
- the moisture uptake is calculated as follows:
- the wet mass is the mass measured before the residence time in the enclosure and the passage to the oven.
- the dry mass is the mass measured after the residence time in the enclosure and the passage to the oven.
- EXAMPLE 9 Observation with a transmission electron microscope (magnification 5000) of a wire formed by the material produced by extrusion as described in Example 6, from PA66 loaded to the extent of 5% by weight with PAHB according to example 1
- FIG. 3 shows the result of the observation. It appears from this FIG. 3 that the functionalized PAHB additive is in the form of differentiated nodules of average size less than 1 ⁇ m, dispersed in a continuous phase formed by PA66.
- the functionalized PAHB additive mixture + PA66 matrix constitute two phases observable in transmission electron microscopy at high magnification. The functionalized PAHB additive and the matrix are therefore not compatible (immiscible).
- Example 10 MATRIX ADDITIVE COMPATIBILITY (MISCIBILITY) (ref. IM Ward, DW Hadiey, "An introduction to the mechanical propertîes of solid polymers", chap 9, John Wiley et sons, 1993)
- the measurement of the glass transition on dried multifilaments always leads to the value of 77.2 ° C., which proves the non-compatible (immiscible) nature of the PA 66 / PAHB mixtures of Examples 1 to 4.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyamides (AREA)
- Artificial Filaments (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0116321 | 2001-12-17 | ||
FR0116321 | 2001-12-17 | ||
PCT/FR2002/004368 WO2003051993A1 (fr) | 2001-12-17 | 2002-12-16 | Composition thermoplastique comprenant un additif polymere hyperbranche, articles realises a partir de ce materiau |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1456300A1 true EP1456300A1 (fr) | 2004-09-15 |
Family
ID=8870587
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02801134A Withdrawn EP1456300A1 (fr) | 2001-12-17 | 2002-12-16 | Composition thermoplastique comprenant un additif polymere hyperbranche, articles realises a partir de ce materiau |
Country Status (11)
Country | Link |
---|---|
US (1) | US7375165B2 (fr) |
EP (1) | EP1456300A1 (fr) |
JP (1) | JP4191045B2 (fr) |
KR (1) | KR100610544B1 (fr) |
CN (1) | CN1309785C (fr) |
AU (1) | AU2002364841A1 (fr) |
BR (1) | BR0215143A (fr) |
CA (1) | CA2470166C (fr) |
RU (1) | RU2307137C2 (fr) |
TW (1) | TWI280966B (fr) |
WO (1) | WO2003051993A1 (fr) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE405611T1 (de) * | 2004-10-08 | 2008-09-15 | Rhodia Chimie Sa | Verfahren zur herstellung von partikeln aus thermoplastischen polymeren und daraus gewonnenes pulver |
CN101291994B (zh) * | 2005-10-25 | 2012-05-23 | 国立大学法人九州大学 | 表面和/或界面改性了的聚合物结构体、及其制造方法 |
FR2899591B1 (fr) * | 2006-04-10 | 2008-05-23 | Rhodia Recherches & Tech | Procede de preparation de particules a base de polymere thermoplastique et poudre ainsi obtenue |
DE102008026075B4 (de) * | 2008-05-30 | 2015-04-30 | Lurgi Zimmer Gmbh | Verfahren zur Herstellung von Polyamiden unter Verwendung von Carbonsäuren und Amiden |
US20100113669A1 (en) * | 2008-10-30 | 2010-05-06 | E.I. Du Pont De Nemours And Company | Thermoplastic composition including hyperbranched aromatic polyamide |
US8293831B2 (en) * | 2008-10-30 | 2012-10-23 | E I Du Pont De Nemours And Company | Thermoplastic composition including thermally conductive filler and hyperbranched polyesteramide |
FR2958296B1 (fr) * | 2010-04-06 | 2013-08-16 | Rhodia Operations | Composition polyamide de haute viscosite |
US9061806B2 (en) * | 2012-08-30 | 2015-06-23 | Thomas & Betts International, Llc | Cable ties employing a nylon/graphene composite |
DE102014215547A1 (de) * | 2014-08-06 | 2016-02-11 | Airbus Operations Gmbh | Klebehalter zur Befestigung an einer Struktur |
CN105017526B (zh) * | 2015-08-19 | 2017-09-01 | 常熟理工学院 | 一种增韧增强尼龙6的增容剂及其制备方法和用途 |
CN108586729B (zh) * | 2018-03-26 | 2020-09-22 | 中国石油化工股份有限公司 | 一种支化尼龙的制备方法、复合薄膜及其制备方法 |
CN108559074B (zh) * | 2018-03-26 | 2020-09-25 | 中国石油化工股份有限公司 | 一种支化尼龙6的连续聚合工艺及其产品 |
CN108912383B (zh) * | 2018-07-20 | 2020-11-10 | 西能化工科技(上海)有限公司 | 超高温可膨胀热塑性微球及其应用 |
CN111978506B (zh) * | 2019-05-23 | 2022-08-09 | 珠海瑞杰包装制品有限公司 | 一种水性超支化聚氨酯丙烯酸酯乳液的制备方法、uv固化涂料及其制备方法和应用 |
CN112724667B (zh) * | 2020-12-16 | 2022-06-14 | 金发科技股份有限公司 | 一种聚酰胺模塑组合物及其制备方法和应用 |
CN114716812B (zh) * | 2022-02-17 | 2023-11-07 | 上海金发科技发展有限公司 | 一种mca阻燃聚酰胺复合材料及其制备方法和应用 |
CN114940755B (zh) * | 2022-07-04 | 2024-03-01 | 华润化学材料科技股份有限公司 | 一种聚酰胺弹性体及其制备方法 |
CN115975378B (zh) * | 2022-12-14 | 2023-11-28 | 苏州优利金新材料有限公司 | 一种耐高温的二氧化硅改性尼龙材料的制备方法和应用 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4346024A (en) * | 1979-12-10 | 1982-08-24 | Rhone-Poulenc Industries | Heat-stable polyphase polyamide/polyesteramide compositions |
US4387184A (en) * | 1979-12-10 | 1983-06-07 | Rhone-Poulenc Industries | Heat stable polyphase polyamide compositions and preparation thereof |
SE509240C2 (sv) * | 1996-05-28 | 1998-12-21 | Perstorp Ab | Termoplastisk kompound bestående av en termoplastisk polymer bunden till en dendritisk eller hyperförgrenad makromolekyl samt komposition och produkt därav |
FR2793252B1 (fr) * | 1999-05-05 | 2001-07-20 | Rhodianyl | Copolyamide hyperbranche, composition a base de ce copolyamide hyperbranche et procede d'obtention de ce dernier |
-
2002
- 2002-12-16 WO PCT/FR2002/004368 patent/WO2003051993A1/fr active Application Filing
- 2002-12-16 EP EP02801134A patent/EP1456300A1/fr not_active Withdrawn
- 2002-12-16 JP JP2003552864A patent/JP4191045B2/ja not_active Expired - Fee Related
- 2002-12-16 TW TW091136263A patent/TWI280966B/zh not_active IP Right Cessation
- 2002-12-16 RU RU2004121900/04A patent/RU2307137C2/ru not_active IP Right Cessation
- 2002-12-16 US US10/498,422 patent/US7375165B2/en not_active Expired - Fee Related
- 2002-12-16 CA CA002470166A patent/CA2470166C/fr not_active Expired - Fee Related
- 2002-12-16 KR KR1020047009481A patent/KR100610544B1/ko not_active IP Right Cessation
- 2002-12-16 BR BR0215143-0A patent/BR0215143A/pt active Search and Examination
- 2002-12-16 AU AU2002364841A patent/AU2002364841A1/en not_active Abandoned
- 2002-12-16 CN CNB02827461XA patent/CN1309785C/zh not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO03051993A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2470166C (fr) | 2009-09-08 |
US20050222376A1 (en) | 2005-10-06 |
JP4191045B2 (ja) | 2008-12-03 |
BR0215143A (pt) | 2004-11-03 |
KR20040071731A (ko) | 2004-08-12 |
CN1309785C (zh) | 2007-04-11 |
TW200304477A (en) | 2003-10-01 |
CA2470166A1 (fr) | 2003-06-26 |
RU2307137C2 (ru) | 2007-09-27 |
JP2005513183A (ja) | 2005-05-12 |
TWI280966B (en) | 2007-05-11 |
WO2003051993A1 (fr) | 2003-06-26 |
RU2004121900A (ru) | 2005-04-10 |
AU2002364841A1 (en) | 2003-06-30 |
US7375165B2 (en) | 2008-05-20 |
CN1615341A (zh) | 2005-05-11 |
KR100610544B1 (ko) | 2006-08-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2470166C (fr) | Composition thermoplastique comprenant un additif polymere hyperbranche porteur de fonctions non compatibles, et articles realises a partir de ce materiau | |
CA2470216C (fr) | Composition polymere thermoplastique comprenant un polymere hyperbranche, et articles realises a partir de cette composition | |
EP1183301A1 (fr) | Copolyamide hyperbranche, composition a base de ce copolyamide hyperbranche et procede d'obtention de ce dernier | |
WO2005000963A1 (fr) | Composition à base de matrice polyamide et/ou polyester et articles réalisés à partir de cette composition. | |
WO2011003787A1 (fr) | Article polyamide composite | |
EP2652013A1 (fr) | Copolymere polyamide-polyolefine | |
EP2513203B1 (fr) | Article composite a base de resines polyamides de faibles masses moleculaires | |
WO2016102507A1 (fr) | Melange de polyamides a fluidite amelioree | |
FR2833603A1 (fr) | Composition polymere thermoplastique comprenant un copolyamide hyperbranche, et articles realises a partir de cette composition | |
FR2826661A1 (fr) | Polymere thermoplastique, son application dans des compositions polyamides a hydrophilie et antistaticite ameliorees | |
EP1592748A1 (fr) | Composition comprenant une matrice et un additif fonctionnalise et articles realises a partir de cette composition | |
WO2016102481A1 (fr) | Composition thermoplastique a haute fluidite | |
WO2002012373A1 (fr) | Copolyamides et compositions a base de ces copolyamides | |
EP1649087A2 (fr) | Fils, fibres, filaments resistants a l' abrasion. | |
BE717902A (fr) | ||
MXPA01011205A (en) | Hyperbranched copolyamide, composition based on said hyperbranched copolyamide and method for obtaining same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20040607 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: BORDES, BERTRAND Inventor name: MARCHAND, JEAN-PIERRE Inventor name: ROCHAT, SANDRINE Inventor name: PAULO, CHRISTOPHE Inventor name: VIDIL, CHRISTINE Inventor name: SCHERBAKOFF, NATALIA Inventor name: TOURAUD, FRANCK Inventor name: SASSI, JEAN-FRANEOIS |
|
17Q | First examination report despatched |
Effective date: 20060906 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20130702 |