EP1155065A1 - Polyetheresteramides et compositions de polymeres antistatiques les contenant - Google Patents
Polyetheresteramides et compositions de polymeres antistatiques les contenantInfo
- Publication number
- EP1155065A1 EP1155065A1 EP00968057A EP00968057A EP1155065A1 EP 1155065 A1 EP1155065 A1 EP 1155065A1 EP 00968057 A EP00968057 A EP 00968057A EP 00968057 A EP00968057 A EP 00968057A EP 1155065 A1 EP1155065 A1 EP 1155065A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyamide
- dicarboxylic acid
- acid
- polyetheresteramides
- blocks
- 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.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- 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
Definitions
- the present invention relates to polyetheresteramides (B) having in their chain elements carrying sulfonate groups.
- the polyetheresteramides (B) are copolymers originating from the condensation of polyamide blocks with ends of carboxylic chains with polyetherdiol blocks essentially comprising alkylene oxide units and preferably ethylene oxide units - (C2H4 - O) -.
- the incorporation of elements carrying sulfonate groups in the polyetheresteramide chain makes it possible to improve its intrinsic antistatic properties.
- the present invention also relates to the addition of these polyetheresteramides (B) in thermoplastic polymers (A) to make them antistatic.
- thermoplastic polymer (A) antistatic properties This is to give the thermoplastic polymer (A) antistatic properties.
- the formation and retention of static electricity charges on the surface of most plastics is known.
- the presence of static electricity on thermoplastic films leads for example these films to stick to each other making their separation difficult.
- the presence of static electricity on packaging films can cause the accumulation of dust on the objects to be packaged and thus hinder their use.
- Static electricity can also damage microprocessors or components of electronic circuits.
- Static electricity can also cause the combustion or explosion of flammable materials such as, for example, expandable polystyrene beads that contain pentane.
- antistatic agents such as ionic surfactants of the ethoxylated amino or sulfonate type which are added to polymers.
- antistatic properties of polymers depend on ambient humidity and they are not permanent since these agents migrate to the surface of the polymers and disappear. It was then proposed as antistatic agents copolymers with polyamide blocks and hydrophilic polyether blocks, these agents have the advantage of not migrating and therefore of giving permanent antistatic properties and more independent of ambient humidity.
- US Pat. No. 3,296,204 describes fibers of linear polyamide obtained by the reaction of 5-sulfoisophthalic acid with a diamine followed by polycondensation with an amino acid or a salt of diamine and of diacid such as hexamethylene adipate. These fibers have good dyeability and absorb moisture like natural fibers. They are not polyetheresteramides.
- Patent application JP 11 029 685 A published on February 2, 1999 describes antistatic acrylic resins containing polyetheresters obtained by condensation of polyoxyalkylene glycol and dicarboxylic acids. Some of these diacids contain sulfonic groups. These polyetheresters are not polyetheresteramides.
- Patent application JP 08 208 830 A published on August 13, 1996 describes hydrophilic elastomers containing salts of 5-sulfoisophthalic acid and adducts of ethylene oxide on an aromatic diol. Polyetheresteramides are not clearly described. It is not described blocks consisting of copolyamide or oligomers of polyamide of low molecular weights.
- US Pat. No. 5,096,995 describes polyetheresteramides having two types of polyether blocks, namely polyether blocks of polyethylene glycol type and blocks which are adducts of ethylene oxide on an aromatic diol.
- the chain limiter of the polyamide blocks is a dicarboxylic acid, it is mentioned diacids carrying a sulfonate group such as the sodium salt of 3-sulfoisophthalic acid and unsubstituted diacids but it is prefers to use unsubstituted acids such as terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid and decanedicarboxylic acid.
- Patent application JP 05 140 541 A published on June 8, 1993 describes polyetheresteramides having polyamide blocks formed by the condensation of caprolactam in the presence of the sodium salt of 3-sulfoisophthalic acid and polyether blocks which are adducts of l ethylene oxide on bisphenol A. It is not described blocks consisting of copolyamide or oligomers of polyamide of low molecular weights.
- Patent EP 613 919 describes polyetheresteramides having polyether blocks which are adducts of ethylene oxide on bisphenol A.
- the chain limiter of the polyamide blocks is a dicarboxylic acid, it is mentioned of the diacids carrying a sulfonate group such than the sodium salt of 3-sulfoisophthalic acid and unsubstituted diacids such as terephthalic acid, isophthalic acid, sebacic acid, adipic acid and decanedicarboxylic acid. None of the examples uses diacids carrying sulfonate groups.
- polyetheresteramides having polyamide blocks comprising sulfonates of dicarboxylic acids either as chain limiters of the polyamide block or associated with a diamine as one of the constituent monomers of the polyamide block .
- the polyether blocks consist essentially of alkylene oxide units, preferably ethylene oxide, but do not include aromatic diols, that is to say that it is advantageously polyethylene glycol.
- the Applicant has found new polyetheresteramides having polyamide blocks of the oligomeric type of low molecular weight polyamide or of the copolyamide type which comprise sulfonates of dicarboxylic acids and whose polyether blocks are adducts of alkylene oxide, preferably ethylene oxide, on an aromatic diol. This combination is particularly advantageous for improving the thermal resistance.
- the applicant has found that the polyetheresteramides of the first and second form of the invention are particularly useful for rendering a thermoplastic polymer (A) antistatic.
- the present invention relates to polyetheresteramides (B) having polyamide blocks comprising sulfonates of dicarboxylic acids either as chain limiters of the polyamide block or associated with a diamine as one of the constituent monomers of the polyamide block and having polyether blocks consisting essentially of alkylene oxide units.
- the present invention relates to polyetheresteramides (B) having polyamide blocks of the oligomer type of low molecular weight polyamide or copolyamide type which include sulfonates of dicarboxylic acids and having polyether blocks which are adducts of alkylene oxide on an aromatic diol.
- the present invention relates to anti-static or non-breathable polymer compositions comprising a thermoplastic polymer (A) and at least one polyetheresteramide (B) according to one of the preceding forms.
- Dicarboxylic acid sulfonates are alkali metal or ammonium salts of aromatic diacids. These are, for example, sodium, potassium, lithium and ammonium salts of acids and / or alkyl esters of 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, 5-sulfoisophthalic acid (3- sulfoisophthalic), 2-sulfotherephthalic acid, 2,6-dicarboxynaphthalene-4-sulfonic acid, 2,7-dicarboxynaphthalene-4-sulfonic acid and diphenylsulfoterephthalic acid.
- Polyetheresteramides (B) are polymers containing polyamide blocks and polyether blocks which result from the copolycondensation of dicarboxylic polyamide sequences (at the ends of carboxylic chains) with polyetherdiols.
- polyamide sequences with dicarboxylic chain ends originate, for example, from the condensation of alpha-omega aminocarboxylic acids, lactams or dicarboxylic acids and diamines in the presence of a chain-limiting dicarboxylic acid.
- the number-average molar mass Mn of the polyamide blocks is between 300 and 15,000 and preferably between 400 and 5,000.
- the mass Mn of the polyether blocks is between 100 and 6,000 and preferably between 200 and 3,000.
- polyamide blocks and polyether blocks can also include patterns distributed randomly. These polymers can be prepared by the simultaneous reaction of polyether and precursors of polyamide blocks.
- polyetherdiol, a lactam (or an alpha-omega amino acid) and a chain-limiting diacid can be reacted in the presence of a little water.
- a polymer is obtained which essentially has polyether blocks, polyamide blocks of very variable length, but also the various reactants which have reacted randomly which are distributed statistically along the polymer chain.
- polymers containing polyamide blocks and polyether blocks whether they originate from the copolycondensation of polyamide and polyether blocks prepared beforehand or from a one-step reaction have, for example, an inherent viscosity between 0.4 and 2.5 measured in metacresol at 25 ° C for an initial concentration of 0.5 g / 100 ml.
- the polyamide sequences with dicarboxylic chain ends originate from the condensation either of alpha-omega aminocarboxylic acids or of lactams or of dicarboxylic acids and diamines in the presence of a chain-limiting dicarboxylic acid. If the polyamide block is formed by reaction of a diacid and a diamine, the chain limiter may be the diacid used in excess or another diacid.
- the excess dicarboxylic acid used as chain limiter or the dicarboxylic acid used as chain limiter is wholly or partly a dicarboxylic acid sulfonate.
- alpha omega aminocarboxylic acids mention may be made of aminoundecanoic acid, by way of example of lactam, mention may be made of caprolactam and lauryllactam, as example of dicarboxylic acid, mention may be made of adipic acid.
- decanedioic acid and dodecanedioic acid, as an example of diamine can be cite hexamethylene diamine.
- the polyamide blocks are made of polyamide12, of polyamide 6 or of polyamide 6-6 and preferably of PA 6 or of PA 12 and the limiter is SIPNA (sodium salt of 5-sulfoisophthalic acid).
- the melting point of these polyamide blocks, which is also that of the copolymer (B), is generally 10 to 15 ° C. below that of PA 12 or PA 6.
- the polyamide sequences are oligomers which result from the condensation of one or more alpha omega aminocarboxylic acids and / or of one or more lactams having from 6 to 12 carbon atoms in the presence of an acid sulfonate.
- alpha omega aminocarboxylic acid mention may be made of aminoundecanoic acid and aminododecanoic acid.
- dicarboxylic acid having from 6 to 12 carbon atoms mention may be made of adipic acid, sebacic acid, isophthalic acid, butanedioic acid, 1,4 cyclohexyldicarboxylic acid, terephthalic acid, dimerized fatty acids (these dimerized fatty acids have a dimer content of at least 98% and are preferably hydrogenated) and dodecanedioic acid.
- a lactam mention may be made of caprolactam and lauryllactam. Polyamide sequences obtained by condensation of lauryllactam in the presence of SIPNA and of mass Mn 750 have a melting temperature of 127-130 ° C.
- the polyamide sequences result from the condensation of at least one alpha omega aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.
- the chain limiter can be an excess of the acid dicarboxylic or another dicarboxylic acid, all or part of the chain limiter being replaced by a dicarboxylic acid sulfonate.
- the amount of dicarboxylic acid sulfonate may be greater than the amount necessary as a chain limiter and even replace all or part of the dicarboxylic acids used in combination with the diamine to constitute the polyamide block of this third type.
- the alpha omega aminocarboxylic acid, the lactam and the dicarboxylic acid can be chosen from those mentioned above.
- the diamine can be an aliphatic diamine having from 6 to 12 atoms, it can be arylic and / or cyclic saturated.
- hexamethylenediamine piperazine, ⁇ -aminoethylpiperazine, bisaminopropylpiperazine, tetramethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine, 1.5 diaminohexane, 2.2, 4-trimethyl-1, 6-diamino-hexane, polyols diamine, isophorone diamine (IPD), methyl pentamethylenediamine (MPDM), bis (aminocyclohexyl) methane (BACM), bis (3-methyl-4 aminocyclohexyl ) methane (BMACM).
- IPD isophorone diamine
- MPDM methyl pentamethylenediamine
- ALM bis (aminocyclohexyl) methane
- BMACM bis (3-methyl-4 aminocyclohexyl ) methane
- the various constituents of the polyamide block and their proportion are chosen to obtain a melting temperature below 150 ° C. and advantageously between 90 and 135 ° C.
- Copolyamides with low melting temperature are described in US Patents 4,483,975, DE 3,730,504, US 5,459,230, the same proportions of the constituents are used for the polyamide blocks of (B).
- (B) can also be the copolymers described in US 5,489,667.
- the polyether blocks can represent 5 to 85% by weight of (B) and advantageously from 15 to 50%.
- the blocks consist of one or more alkylene oxide units distributed in an orderly or random fashion or consist of a mixture of these compounds.
- alkylene oxide of ethylene oxide, propylene oxide and tetrahydrofuran.
- essentially ethylene oxide is used.
- PEG blocks that is to say those made up of ethylene oxide units
- PPG blocks that is to say those made up of ethylene oxide units.
- propylene and PTMG blocks ie those consisting of tetramethylene glycol units also called polytetrahydrofuran.
- the polyetheresteramides have polyamide blocks identical to those of the polyetheresteramides of the second and third type of the first form.
- the polyether blocks are adducts of alkylene oxide on an aromatic diol.
- Z-] and Z2 are chosen from alkyl groups having from 1 to 4 carbon atoms, aralkyl groups having from 6 to 10 carbon atoms, aryl groups and halogens; Z- ⁇ and ⁇ 2 may be the same or different; Y is a covalent bond, an alkylidene group, an arylalkylidene group, an oxygen atom, a sulfur atom, a sulfonyl group, a bistrifluoromethylmethylene group or a carbonyl group; n and m are integers from 0 to 4.
- the polyetheresteramides according to the first and second form of the invention can be prepared by any means allowing the polyamide blocks and the polyether blocks to be attached. In practice, essentially two methods are used, one said in 2 steps, the other in one step. In the description processes the general expressions of chain limiter and polyamide precursor are used without detailing their exact nature, knowing that they have been described above in the description of polyetheresteramides.
- the 2-step process consists first of all in preparing the polyamide blocks with carboxylic ends by condensation of the polyamide precursors in the presence of a chain-limiting dicarboxylic acid, then in a second step in adding the polyether and a catalyst.
- the reaction is usually carried out between 180 and 300 ° C, preferably 200 to 260 ° C for about 2 hours.
- the pressure in the reactor can for example be between 5 and 30 bars. The pressure is slowly reduced by putting the reactor into the atmosphere and then the excess water is distilled, for example an hour or two.
- the polyamide with carboxylic acid ends having been prepared, the polyether and a catalyst are then added.
- the polyether can be added one or more times, as can the catalyst.
- the polyether is first added, the reaction of the OH ends of the polyether and of the COOH ends of the polyamide begins with ester bond formations and elimination of water; Water is removed as much as possible from the reaction medium by distillation and then the catalyst is introduced to complete the bonding of the polyamide blocks and of the polyether blocks.
- This second step is carried out with stirring preferably under a vacuum of at least 5 mm Hg (650 Pa) at a temperature such that the reagents and the copolymers obtained are in the molten state.
- this temperature can be between 100 and 400 ° C.
- the reaction is followed by measuring the torsional torque exerted by the molten polymer on the agitator or by measuring the electric power consumed by the agitator. The end of the reaction is determined by the value of the target torque or power.
- the catalyst is defined as being any product making it possible to facilitate the bonding of the polyamide blocks and of the polyether blocks by esterification.
- the catalyst is advantageously a derivative of a metal (M) chosen from the group formed by titanium, zirconium and hafnium.
- M represents titanium, zirconium or hafnium and R, identical or different, denote alkyl radicals, linear or branched, having from 1 to 24 carbon atoms.
- C- alkyl radicals to C24 from which are chosen the radicals R of the tetraalkoxides used as catalysts in the process according to the invention are for example such as methyl, ethyl, propyl, isopropyl, butyl, ethylhexyl, decyl, dodecyl, hexadodecyl.
- the preferred catalysts are the tetraalkoxides for which the radicals R, identical or different, are alkyl radicals C-
- Examples of such catalysts are in particular Z r (OC2H 5 ) 4, Z r (0-isoC3H7) 4, Z r (OC4Hg) 4, Z r (OC5H-
- the catalyst used in this process according to the invention can consist solely of one or more of the tetraalkoxides of formula M (OR) 4 defined above. It can also be formed by the association of one or more of these tetraalkoxides with one or more alkali or alkaline-earth alcoholates of formula (R-
- Y represents an alkali or alkaline earth metal and p is the valence of Y.
- the amounts of alkali or alkaline earth alcoholate and of zirconium or hafnium tetraalkoxides which are combined to constitute the mixed catalyst can vary within wide limits limits. However, it is preferred to use amounts of alcoholate and tetraalkoxides such that the molar proportion of alcoholate is substantially equal to the molar proportion of tetraalkoxide.
- the proportion by weight of catalyst that is to say of the tetraalkoxide (s) when the catalyst does not contain alkali or alkaline earth alcoholate or of all of the tetraalkoxide (s) and of alkaline or alkaline alcoholate (s) earthy when the catalyst is formed by the association of these two types of compounds, advantageously varies from 0.01 to 5% of the weight of the mixture of the polyamide dicarboxylic with the polyoxyalkylene glycol, and is preferably between 0.05 and 2% of this weight.
- salts of the metal (M) in particular the salts of (M) and of an organic acid and the complex salts between the oxide of (M) and / or l hydroxide of (M) and an organic acid.
- the organic acid can be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauryac acid, acid myristic, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, cyclohexane carboxylic acid, phenylacetic acid, benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid and crotonic acid.
- Acetic and propionic acids are particularly preferred.
- M is zirconium.
- zirconyl salts These salts can be called zirconyl salts.
- the Applicant without being bound by this explanation, believes that these zirconium and organic acid salts or the complex salts mentioned above release ZrO ++ during the process.
- the product sold under the name of zirconyl acetate is used.
- the quantity to be used is the same as for the derivatives M (OR) 4.
- all the reagents used in the two-step process are mixed, that is to say the polyamide precursors, the chain-limiting dicarboxylic acid, the polyether and the catalyst. These are the same reagents and the same catalyst as in the two-step process described above.
- the reactor is closed and heated with stirring as in the first step of the two-step process described above.
- the reaction is followed as above for the two-step process.
- the catalyst used in the one-step process is preferably a salt of the metal (M) and an organic acid or a complex salt between the oxide of (M) and / or the hydroxide of (M) and an acid organic.
- polymers (A) mention may be made of polyolefins, polyamides, fluorinated polymers, saturated polyesters, polycarbonate, styrene resins, PMMA, polyurethanes thermoplastics (TPU), PVC, copolymers of ethylene and vinyl acetate (EVA), copolymers of ethylene and an alkyl (meth) acrylate, ABS, SAN, polyacetal and polyketones.
- Polyolefins within the meaning of the invention also denote the copolymers of ethylene and of an alpha olefin. It would not be departing from the scope of the invention to use a mixture of two or more polymers (A). With regard to the proportions of (A) and (B) the amount of (B) depends on the level of antistatism required and on the proportion of polyether in (B). The proportion of (A) and (B) varies from 2 to 40 parts of (B) for 98 to 60 parts of (A), advantageously 2 to 20 parts of (B) are used for 98 to 80 parts of (A) .
- compositions according to the invention may also contain at least one additive chosen from: fillers (mineral, fire-resistant, etc.), fibers, inorganic and / or organic and / or polyeectrolyte salts - dyes; pigments; brighteners; antioxidants; UV stabilizers.
- fillers mineral, fire-resistant, etc.
- fibers inorganic and / or organic and / or polyeectrolyte salts - dyes
- pigments pigments
- brighteners antioxidants
- UV stabilizers UV stabilizers.
- the compositions of the invention are prepared by the usual techniques of thermoplastics such as for example by extrusion or using twin-screw mixers.
- AA chain limiter (example A1 (example SIPNa SIPNa SIPNa SIPNa outside the invention) Outside the invention)
- AA adipic acid
- SIPNa sodium salt of sulphoisophthalic acid
- Example 7 we first describe Example 7 before Example 6.
- Example 6 the procedure is as in Example 7 but without using SIPNA.
- Examples 8 and 9 the procedure is as in Example 7 but by modifying the catalyst and / or the proportion of SIPNA and / or the proportion of PEG.
- Table 2 Composition and resistivity of Examples 6 - 9 polyetheresteramide limited by SIPNa
- SIPNa (% by weight) 0 9.4 9.4 7.1
- SIPNa sodium salt of sulphoisophthalic acid
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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FR9912956 | 1999-10-18 | ||
FR9912956 | 1999-10-18 | ||
PCT/FR2000/002889 WO2001029113A1 (fr) | 1999-10-18 | 2000-10-17 | Polyetheresteramides et compositions de polymeres antistatiques les contenant |
Publications (1)
Publication Number | Publication Date |
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EP1155065A1 true EP1155065A1 (fr) | 2001-11-21 |
Family
ID=9551039
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00968057A Ceased EP1155065A1 (fr) | 1999-10-18 | 2000-10-17 | Polyetheresteramides et compositions de polymeres antistatiques les contenant |
Country Status (8)
Country | Link |
---|---|
US (2) | USRE39994E1 (fr) |
EP (1) | EP1155065A1 (fr) |
JP (1) | JP2003512487A (fr) |
KR (1) | KR100629122B1 (fr) |
CN (1) | CN1210330C (fr) |
AU (1) | AU7801800A (fr) |
CA (1) | CA2355705C (fr) |
WO (1) | WO2001029113A1 (fr) |
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WO2011124833A1 (fr) | 2010-04-07 | 2011-10-13 | Arkema France | Copolymere a blocs issu de matieres renouvelables et procede de fabrication d'un tel copolymere a blocs |
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DE60026262T2 (de) | 1999-04-23 | 2007-02-15 | Arkema | Antistatische Polymerzusammensetzungen |
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2000
- 2000-10-17 US US11/376,699 patent/USRE39994E1/en not_active Expired - Fee Related
- 2000-10-17 AU AU78018/00A patent/AU7801800A/en not_active Abandoned
- 2000-10-17 WO PCT/FR2000/002889 patent/WO2001029113A1/fr not_active Application Discontinuation
- 2000-10-17 US US09/868,099 patent/US6706851B1/en not_active Ceased
- 2000-10-17 JP JP2001531905A patent/JP2003512487A/ja not_active Abandoned
- 2000-10-17 CN CNB008022801A patent/CN1210330C/zh not_active Expired - Fee Related
- 2000-10-17 KR KR1020017007671A patent/KR100629122B1/ko not_active IP Right Cessation
- 2000-10-17 CA CA002355705A patent/CA2355705C/fr not_active Expired - Fee Related
- 2000-10-17 EP EP00968057A patent/EP1155065A1/fr not_active Ceased
Non-Patent Citations (1)
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Cited By (19)
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EP2090629A2 (fr) | 2008-02-15 | 2009-08-19 | Arkema France | Utilisation d'un promoteur d'adhérence dans une solution de nettoyage |
EP3660076A1 (fr) | 2008-10-06 | 2020-06-03 | Arkema France | Copolymère à blocs issu de matières renouvelables et procédé de fabrication d'un tel copolymère à blocs |
EP3196226A1 (fr) | 2008-10-06 | 2017-07-26 | Arkema France | Copolymère à blocs issu de matières renouvelables et procédé de fabrication d'un tel copolymère à blocs |
WO2010086574A2 (fr) | 2009-02-02 | 2010-08-05 | Arkema France | Procede de synthese d'un alliage de copolymere a blocs presentant des proprietes antistatiques ameliorees |
EP2502950A1 (fr) | 2009-02-02 | 2012-09-26 | Arkema France | Procédé de synthèse d'un alliage de copolymère à blocs présentant des propriétés antistatiques améliorées |
WO2011073356A2 (fr) | 2009-12-17 | 2011-06-23 | L'oreal | Utilisation d'une composition cosmétique comprenant au moins un polymère élastomère filmogène pour traiter la transpiration humaine |
EP3085725A1 (fr) | 2010-04-07 | 2016-10-26 | Arkema France | Copolymère à blocs issu de matières renouvelables et procédé de fabrication d'un tel copolymère à blocs |
WO2011124833A1 (fr) | 2010-04-07 | 2011-10-13 | Arkema France | Copolymere a blocs issu de matieres renouvelables et procede de fabrication d'un tel copolymere a blocs |
WO2011151203A2 (fr) | 2010-06-03 | 2011-12-08 | L'oreal | Processus de traitement cosmétique utilisant un revêtement à base d'un copolymère contenant des blocs de polyamide et des blocs de polyéther |
WO2012084848A1 (fr) | 2010-12-23 | 2012-06-28 | Bayer Materialscience Ag | Matières moulables antistatiques à base de polycarbonate |
WO2012120114A1 (fr) | 2011-03-09 | 2012-09-13 | L'oreal | Procédé de traitement cosmétique de la transpiration humaine qui comprend l'application d'un film polymère antiperspirant solubilisable |
WO2017186690A1 (fr) | 2016-04-27 | 2017-11-02 | Covestro Deutschland Ag | Masses de moulage thermoplastiques, antistatiques et stables à la lumière en polycarbonate |
WO2017186663A1 (fr) | 2016-04-27 | 2017-11-02 | Covestro Deutschland Ag | Masses moulées thermoplastiques antistatiques |
US10655011B2 (en) | 2016-04-27 | 2020-05-19 | Covestro Deutschland Ag | Antistatic and light-stable thermoplastic polycarbonate moulding compounds |
US11352494B2 (en) | 2016-04-27 | 2022-06-07 | Covestro Deutschland Ag | Anti-static thermoplastic molding materials |
WO2020240133A1 (fr) | 2019-05-27 | 2020-12-03 | Arkema France | Copolyesteramide auto-ignifuge |
FR3096683A1 (fr) | 2019-05-27 | 2020-12-04 | Arkema France | copolyesteramide auto-ignifugé |
WO2020240132A1 (fr) | 2019-05-29 | 2020-12-03 | Arkema France | Copolymère à blocs à résistance améliorée au sébum |
FR3096684A1 (fr) | 2019-05-29 | 2020-12-04 | Arkema France | Copolymère à blocs à résistance améliorée au sébum |
Also Published As
Publication number | Publication date |
---|---|
WO2001029113A1 (fr) | 2001-04-26 |
CN1210330C (zh) | 2005-07-13 |
US6706851B1 (en) | 2004-03-16 |
USRE39994E1 (en) | 2008-01-01 |
AU7801800A (en) | 2001-04-30 |
KR100629122B1 (ko) | 2006-09-27 |
KR20010082367A (ko) | 2001-08-29 |
CA2355705C (fr) | 2007-04-24 |
CA2355705A1 (fr) | 2001-04-26 |
JP2003512487A (ja) | 2003-04-02 |
CN1327461A (zh) | 2001-12-19 |
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