EP1994077A2 - Novel use of a copolymer comprising polyamide blocks and polyether blocks originating at least partially from polytrimethylene ether glycol - Google Patents
Novel use of a copolymer comprising polyamide blocks and polyether blocks originating at least partially from polytrimethylene ether glycolInfo
- Publication number
- EP1994077A2 EP1994077A2 EP07731641A EP07731641A EP1994077A2 EP 1994077 A2 EP1994077 A2 EP 1994077A2 EP 07731641 A EP07731641 A EP 07731641A EP 07731641 A EP07731641 A EP 07731641A EP 1994077 A2 EP1994077 A2 EP 1994077A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- blocks
- polyamide
- copolymer
- ether glycol
- use according
- 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- Withdrawn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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000004952 Polyamide Substances 0.000 title claims abstract description 42
- 229920002647 polyamide Polymers 0.000 title claims abstract description 42
- 229920001577 copolymer Polymers 0.000 title claims abstract description 27
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 26
- 229920000570 polyether Polymers 0.000 title claims abstract description 26
- -1 polytrimethylene Polymers 0.000 title claims abstract description 24
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004698 Polyethylene Substances 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 238000009792 diffusion process Methods 0.000 claims abstract description 7
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 6
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 6
- 239000004743 Polypropylene Substances 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims abstract description 4
- 229920000573 polyethylene Polymers 0.000 claims abstract description 4
- 229920001155 polypropylene Polymers 0.000 claims abstract description 4
- 150000004985 diamines Chemical class 0.000 claims description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 150000003951 lactams Chemical class 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 150000001413 amino acids Chemical class 0.000 claims description 5
- 239000007859 condensation product Substances 0.000 claims description 4
- 229920006147 copolyamide elastomer Polymers 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 10
- 229920002614 Polyether block amide Polymers 0.000 description 7
- VPRUMANMDWQMNF-UHFFFAOYSA-N phenylethane boronic acid Chemical compound OB(O)CCC1=CC=CC=C1 VPRUMANMDWQMNF-UHFFFAOYSA-N 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000004427 diamine group Chemical group 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical class C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- XDOLZJYETYVRKV-UHFFFAOYSA-N 7-Aminoheptanoic acid Chemical compound NCCCCCCC(O)=O XDOLZJYETYVRKV-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- OTKFKCIRTBTDKK-UHFFFAOYSA-N [3-(aminomethyl)-5-bicyclo[2.2.1]heptanyl]methanamine Chemical compound C1C(CN)C2C(CN)CC1C2 OTKFKCIRTBTDKK-UHFFFAOYSA-N 0.000 description 1
- YMUAXKYTHNCMAS-UHFFFAOYSA-N [butyl(nitroso)amino]methyl acetate Chemical compound CCCCN(N=O)COC(C)=O YMUAXKYTHNCMAS-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007278 cyanoethylation reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920006017 homo-polyamide Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
Definitions
- the present invention relates to a new use of a copolymer comprising polyamide blocks and polyether blocks, the latter being at least partly polytrimethylene ether glycol (abbreviated PO3G).
- a copolymer comprising polyamide blocks and polyether blocks, the latter being at least partly polytrimethylene ether glycol (abbreviated PO3G).
- polyether block blocks In polyether block blocks (PEBA), polyamide blocks are known to be rigid segments while polyether blocks are flexible segments.
- PA Polyamide block copolymers
- PE polyether blocks
- PEBA PA and PE block copolymers
- the polyamide sequences with dicarboxylic chain ends come for example from the condensation of polyamide precursors in the presence of a chain-control dicarboxylic acid.
- the polyamide blocks with diamine chain ends come for example from the condensation of polyamide precursors in the presence of a chain-regulating diamine.
- the polyamide block and polyether block polymers may also comprise randomly distributed units. Said polymers can be prepared by the simultaneous reaction of the polyether and the precursors of the polyamide blocks.
- polyetherdiol, polyamide precursors, and a chain-regulating diacid can be reacted or polyetherdiamine, polyamide precursors, and a chain-regulating diacid can be reacted.
- a polymer having essentially polyether blocks is obtained, polyamide blocks of very variable length depending on the moment in which the chain regulator intervenes during the formation of the PA block, but also the various reagents reacted randomly which are distributed in a Random (statistical) along the polymer chain.
- the polyamide block may consist of a "homopolyamide” structure [polymerization of a single monomer, ie a single lactam, a single amino acid CC or a single pair (diacid, diamine)] or else of a "copolyamide” type structure. with the polymerization of a mixture of at least two monomers selected from the three types mentioned in the previous case.
- the polyamide blocks are obtained in the presence of a diacid or a chain-control diamine depending on whether polyamide blocks with acid or amine ends are desired. If the precursors already comprise a diacid or a diamine, it suffices, for example, to use it in excess, but it is also possible to use another diacid or another diamine taken from the dicarboxylic acid and diamine groups defined below.
- French patent application FR 88 15441 discloses a waterproof breathable film based on polyetheresteramide, in particular PA 12 - polytetramethylene glycol (PTMG).
- PTMG polytetramethylene glycol
- Another problem is the too low water uptake and the reduction of the water vapor permeability.
- WO97 / 26020 discloses scented resins consisting of a polyetheresteramide type polymer resin for the regular diffusion of volatile substances. This document does not disclose selective diffusion of gases.
- thermoplastic polymer compositions comprising a polyamide and at least one PEBA which is a hydrophilic modifier and / or antistaticity modifier.
- EP0476963 relates to a polymer mixture comprising PEBA with polyether blocks predominant in PEG, and a polyether block PEBA containing no PEG but based on PTMG or PPG.
- the PO3G-based PEBA polymer according to the invention not only has properties for improving the insulating matrix resistivity but also properties:
- PA represents a polyamide block
- PE represents a polyether block
- n represents the number of units -PA-PE- of said copolymer, and in which said blocks come either entirely from polytrimethylene ether glycol (PO 3 G) or else come from a mixture or a copolymer of PO3G and at least one of polyethylene ether glycol (PEG), polypropylene ether glycol (PPG), polytetramethylene ether glycol (PTMG), polyhexamethylene ether glycol and copolymers of tetrahydrofuran (THF) and 3- alkyl tetrahydrofuran (3MeTHF); as breathable product or as an additive imparting breathability properties to thermoplastic polymers to form a selective diffusion membrane depending on the nature of the gas; as an additive to polyamide 6, polyamide 6.6 or copolyamide based on 6 / 6.6 to be converted into a film to improve the mechanical properties and / or processability of said polyamide.
- PEG polyethylene ether glyco
- said PE blocks have a molecular weight ⁇ 800.
- said PE blocks have a molecular weight of at least 250.
- said PE blocks have a molecular mass of between 250 and 650.
- the copolymer is characterized in that at least 10%, preferably at least 20%, even more preferably at least 30%, advantageously at least 50%, still more advantageously at least 75% and, more preferably, 85 to 100% by weight of the PE blocks are from polytrimethylene ether glycol (% by weight based on the total weight of said PE blocks).
- the percentage by weight of PA blocks relative to the total weight of said copolymer is in particular at least 10%, more preferably at least 15%, and preferably up to 90%, more preferably between 40 and 60%.
- the PA blocks have in particular a number-average molecular mass of at least 300, preferably at least 600, and preferably ranging up to 10,000, more preferably up to 5000, and even more preferably up to at 3000.
- n is 1, being in particular at least 5, more preferably at least 6, and up to an average of 60, preferably up to an average of 30, so more preferred up to an average of 25.
- the PA blocks are in particular carboxylic ends so that the bonds between the PA and PE blocks are ester bonds.
- the PA blocks having carboxylic end groups may be the condensation product of a lactam, in particular a lactam C 4 -C 4, an amino acid, in particular an amino acid, C 4 -C 4 or a combination of both with a dicarboxylic acid, in particular a C 4 -C 20 dicarboxylic acid;
- lactams examples include caprolactam, oenantholactam and lauryllactam.
- amino acids examples include aminocaproic acid, amino-7-heptanoic acid, amino-11-undecanoic acid and amino-12-dodecanoic acid.
- dicarboxylic acids examples include 1,4-cyclohexyldicarboxylic acid, butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic and terephthalic and isophthalic acids, but also dimerized fatty acids.
- the carboxyl-terminated PA blocks may also be the condensation product of a dicarboxylic acid such as a C 4 -C 20 alkyl dicarboxylic acid and a diamine, especially a C 2 -C 20 diamine.
- a dicarboxylic acid such as a C 4 -C 20 alkyl dicarboxylic acid and a diamine, especially a C 2 -C 20 diamine.
- diamines mention may be made of hexamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, isomers of bis (4-aminocyclohexyl) methane (BACM), bis (3-methyl-4-aminocyclohexyl) methane (BMACM), and 2-2-bis- (3-methyl-4-aminocyclohexyl) -propane (BMACP), and para-amino-di-cyclohexyl-methane (PACM), and isophoronediamine (IPDA), 2,6-bis (aminomethyl) norbornane (BAMN) and piperazine.
- BCM bis (4-aminocyclohexyl) methane
- BMACM bis (3-methyl-4-aminocyclohexyl) methane
- BMACP 2-2-bis- (3-methyl-4-aminocyclohexyl) -propane
- PAMN para-
- the PA blocks can be chosen from the blocks PA 6, PA 11, PA 12, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 6.14, PA 6.18, PA Pip.10 and PA 9.6.
- the PE blocks come either entirely from polytrimethylene ether glycol (PO3G) or they also advantageously come from PO3G and from at least one of polyethylene ether glycol (PEG), polypropylene ether glycol (PPG), polytetramethylene ether glycol (PTMG), polyhexamethylene ether glycol and copolymers of tetrahydrofuran (THF) and 3-alkyl tetrahydrofuran (3MeTHF). It is also possible to envisage a PE block of "copolyether” type containing a series of PE blocks of the types mentioned above. The chain ends of the copolyethers can be diOH, diNH 2, diisocyanate or diacid according to their synthesis process.
- the polyether glycols in addition to PO3G in the PE block have an average molecular weight such that the PE block the containers have an average molecular weight of at least about 800, more preferably at least about 1000, and preferably at least about 1500. Also, preferably at least about 50% by weight, more preferably at least about less than 75% by weight, and more preferably about 85 to 100% by weight, of the polyether glycol used to form the PE block is PO3G.
- the present invention relates more specifically to the use of a copolymer of formula (I) as defined above as an antistatic product or as an additive imparting antistatic properties to thermoplastic polymers such as polyamides or elastomers.
- the present invention also relates more particularly to the use of a copolymer of formula (I) as defined above as a breathable product or as an additive imparting properties of breathability to thermoplastic polymers such as polyamides. or elastomers.
- the present invention also relates more particularly to the use of a copolymer of formula (I) as defined above to form a selective diffusion membrane depending on the nature of the gas.
- the copolymer of formula (I) can be used as an additive to polyamide 6, polyamide 6.6 or a copolyamide based on 6 / 6.6 to be converted into a film to improve the mechanical properties and / or the the transformation of polyamide.
- the copolymers of the invention may be prepared by any means for hanging the polyamide blocks and the polyether blocks.
- essentially two methods are used, one said in two steps, the other in one step.
- the polyamide blocks are first manufactured and then, in a second step, polyamide blocks and polyether blocks.
- the polyamide precursors, the chain regulator (or the dicarboxylic acid or stoichiometric excess diamine) and the polyether are mixed; a polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reagents reacted in a random manner which are distributed randomly (statistically) along the polymer chain.
- Catalysts described in US Pat. Nos. 4,331,786, 4,155,475, 4,195,155, 4,839,441, 4,884,014, 4,230,838 and 4,332,920 can be used.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
The invention relates to a copolymer comprising polyamide blocks and polyether blocks having general formula (I) -[PA - PE]n- , wherein: PA represents a polyamide block, PE represents a polyether block, and n represents the number of -PA-PE- units in said copolymer. The aforementioned blocks originate either entirely from polytrimethylene ether glycol (PO3G) or from a mixture or a copolymer of PO3G and at least one of the following: polyethylene ether glycol (PEG), polypropylene ether glycol (PPG), polytetramethylene ether glycol (PTMG), polyhexamethylene ether glycol and the copolymers of tetrahydrofurane (THF) and 3-alkyl tetrahydrofurane (3MeTHF). The invention relates to the use of said copolymer as: a breathable-waterproof product or an additive conferring breathable-waterproof properties on thermoplastic polymers in order to form a membrane with selective diffusion as a function of the type of gas; and an additive for polyamide 6, polyamide 6.6 or copolyamide 6/6.6, which is intended to be transformed into a film in order to improve the mechanical properties and/or the processability of the polyamide.
Description
La présente invention porte sur une nouvelle utilisation d'un copolymère comprenant des blocs polyamide et des blocs polyéther, ces derniers étant au moins en partie du polytriméthylène éther glycol (abrégé PO3G) . The present invention relates to a new use of a copolymer comprising polyamide blocks and polyether blocks, the latter being at least partly polytrimethylene ether glycol (abbreviated PO3G).
Dans les blocs polyétherblocamide (PEBA) , les blocs polyamide sont connus pour être des segments rigides tandis que les blocs polyéther sont des segments souples.In polyether block blocks (PEBA), polyamide blocks are known to be rigid segments while polyether blocks are flexible segments.
Les copolymères à blocs polyamide (PA) et blocs polyéthers (PE) ou copolymère à blocs PA et PE, abrégé PEBA, résultent de la copolycondensation de séquences polyamide à extrémités réactives avec des séquences polyéther à extrémités réactives, telles que, entre autres, des:Polyamide block copolymers (PA) and polyether blocks (PE) or PA and PE block copolymers, abbreviated PEBA, result from the copolycondensation of polyamide sequences with reactive ends with polyether sequences with reactive ends, such as, inter alia, :
(1) séquences polyamide à bouts de chaîne diamine avec des séquences polyoxyalkylène à bouts de chaînes dicarboxyliques ou diisocyanate ;(1) diamine chain-end polyamide blocks with polyoxyalkylene blocks having dicarboxylic chain ends or diisocyanate;
(2) séquences polyamide à bouts de chaînes dicarboxyliques avec des séquences polyoxyalkylène à bouts de chaînes diamine obtenues par cyanoéthylation et hydrogénation de séquences polyoxyalkylène alpha-oméga dihydroxylées aliphatiques appelées polyétherdiols ;(2) polyamide sequences having dicarboxylic chain ends with polyoxyalkylene sequences having diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic dihydroxy aliphatic polyoxyalkylene aliphatic sequences known as polyetherdiols;
(3) séquences polyamide à bouts de chaînes dicarboxyliques avec des polyétherdiols, les produits obtenus étant, dans ce cas particulier, des polyétheresteramides .(3) Polyamide sequences with dicarboxylic chain ends with polyetherdiols, the products obtained being, in this particular case, polyetheresteramides.
Les séquences polyamides à bouts de chaînes dicarboxyliques proviennent par exemple de la condensation de précurseurs de polyamides en présence d'un diacide carboxylique régulateur de chaîne.The polyamide sequences with dicarboxylic chain ends come for example from the condensation of polyamide precursors in the presence of a chain-control dicarboxylic acid.
Les séquences polyamides à bouts de chaînes diamine proviennent par exemple de la condensation de précurseurs de polyamides en présence d'une diamine régulateur de chaîne.The polyamide blocks with diamine chain ends come for example from the condensation of polyamide precursors in the presence of a chain-regulating diamine.
Les polymères à blocs polyamide et blocs polyéther peuvent aussi comprendre des motifs répartis de façon aléatoire. Lesdits polymères peuvent être préparés
par la réaction simultanée du polyéther et des précurseurs des blocs polyamide.The polyamide block and polyether block polymers may also comprise randomly distributed units. Said polymers can be prepared by the simultaneous reaction of the polyether and the precursors of the polyamide blocks.
Par exemple, on peut faire réagir du polyétherdiol, des précurseurs de polyamide et un diacide régulateur de chaîne ou on peut aussi faire réagir de la polyétherdiamine, des précurseurs de polyamide et un diacide régulateur de chaîne. On obtient un polymère ayant essentiellement des blocs polyéther, des blocs polyamide de longueur très variable dépendant du moment au cours duquel le régulateur de chaîne intervient durant la formation du bloc PA, mais aussi les différents réactifs ayant réagi de façon aléatoire qui sont répartis de façon aléatoire (statistique) le long de la chaîne polymère.For example, polyetherdiol, polyamide precursors, and a chain-regulating diacid can be reacted or polyetherdiamine, polyamide precursors, and a chain-regulating diacid can be reacted. A polymer having essentially polyether blocks is obtained, polyamide blocks of very variable length depending on the moment in which the chain regulator intervenes during the formation of the PA block, but also the various reagents reacted randomly which are distributed in a Random (statistical) along the polymer chain.
On a avantageusement deux types de blocs polyamide dans les copolymères à blocs PA et PE selon l'invention. Le bloc polyamide peut être constitué d'une structure « homopolyamide » [polymérisation d'1 seul monomère à savoir un seul lactame, un seul C C aminoacide ou un seul couple (diacide, diamine) ] ou alors d'une structure type « copolyamides » avec la polymérisation d'un mélange d'au moins deux monomères pris parmi les trois types cités dans le cas précédent.There are advantageously two types of polyamide blocks in the PA and PE block copolymers according to the invention. The polyamide block may consist of a "homopolyamide" structure [polymerization of a single monomer, ie a single lactam, a single amino acid CC or a single pair (diacid, diamine)] or else of a "copolyamide" type structure. with the polymerization of a mixture of at least two monomers selected from the three types mentioned in the previous case.
Les blocs polyamide sont obtenus en présence d'un diacide ou d'une diamine régulateur de chaîne suivant que l'on souhaite des blocs polyamides respectivement à extrémités acide ou aminé. Si les précurseurs comprennent déjà un diacide ou une diamine il suffit par exemple de l'utiliser en excès mais on peut aussi utiliser un autre diacide ou une autre diamine pris dans les groupes d'acides dicarboxyliques et de diamines définis ci-dessous.The polyamide blocks are obtained in the presence of a diacid or a chain-control diamine depending on whether polyamide blocks with acid or amine ends are desired. If the precursors already comprise a diacid or a diamine, it suffices, for example, to use it in excess, but it is also possible to use another diacid or another diamine taken from the dicarboxylic acid and diamine groups defined below.
On connaît par la demande de brevet français FR 88 15441 un film imper-respirant à base de polyétheresteramide, en particulier de PA 12 - polytétraméthylène glycol (PTMG) . Ces films imper- respirants essentiellement en polyétheresteramides ont l'inconvénient, quand ils sont très perméables, d'avoir une
forte reprise d'humidité qui provoque leur gonflement et les rend fragiles.French patent application FR 88 15441 discloses a waterproof breathable film based on polyetheresteramide, in particular PA 12 - polytetramethylene glycol (PTMG). These essentially breathable waterproof films with polyetheresteramides have the drawback, when they are very permeable, of having a strong moisture uptake which causes their swelling and makes them fragile.
Un autre problème est la reprise en eau trop faible et la réduction de la perméabilité à la vapeur d'eau .Another problem is the too low water uptake and the reduction of the water vapor permeability.
Le document WO97/26020 décrit des résines parfumées constituées d'une résine polymère de type polyetheresteramide permettant la diffusion régulière de substances volatiles. Ce document ne divulgue pas de diffusion sélective des gaz.WO97 / 26020 discloses scented resins consisting of a polyetheresteramide type polymer resin for the regular diffusion of volatile substances. This document does not disclose selective diffusion of gases.
Le document WO02/02696 décrit des compositions de polymère thermoplastique comprenant un polyamide et au moins un PEBA qui est un composé modificateur de 1 'hydrophilie et/ou de 1 'antistaticité .WO02 / 02696 discloses thermoplastic polymer compositions comprising a polyamide and at least one PEBA which is a hydrophilic modifier and / or antistaticity modifier.
Le document EP0476963 est relatif à un mélange de polymères comprenant du PEBA à blocs polyéther majoritaire en PEG, et un PEBA à blocs polyéther ne contenant pas de PEG mais à base de PTMG ou de PPG.The document EP0476963 relates to a polymer mixture comprising PEBA with polyether blocks predominant in PEG, and a polyether block PEBA containing no PEG but based on PTMG or PPG.
La Société déposante a maintenant découvert que les blocs polyéther issus du polytriméthylène éther glycol possèdent de nouvelles utilisations.The Applicant Company has now discovered that polyether blocks derived from polytrimethylene ether glycol have new uses.
Le polymère PEBA à base PO3G selon l'invention présentent en effet non seulement des propriétés d'amélioration de la résistivité de matrice isolante mais également des propriétés :The PO3G-based PEBA polymer according to the invention not only has properties for improving the insulating matrix resistivity but also properties:
(i) imper-respirantes,(i) waterproof-breathable,
(ii) de diffusion sélective de gaz c'est à dire que certain gaz peuvent traverser une menbrane faite avec ledit polymère contrairement à d'autres, et/ou (iii) de modification de propriété mécaniques de polymère ou de compositions de polymères dans lesquelles ils sont ajoutés meilleures que les produits de type PEBA sur base PTMG.
La présente invention a donc pour objet l'utilisation d'un copolymère comprenant des blocs polyamide et des blocs polyéther de formule générale(ii) selective diffusion of gas, that is to say that certain gases can pass through a menbrane made with said polymer in contrast to others, and / or (iii) modification of the mechanical properties of polymer or of polymer compositions in which they are added better than PEBA type products based on PTMG. The subject of the present invention is therefore the use of a copolymer comprising polyamide blocks and polyether blocks of general formula
( \J±)) — ΓιPJrΛA — PJrFIL iJ n—(\ J ±)) - ΓιPJrΛA - PJrFIL iJ n -
dans laquellein which
PA représente un bloc polyamide ; PE représente un bloc polyéther, et n représente le nombre d'unités -PA-PE- dudit copolymère, et dans laquelle lesdits blocs proviennent soit entièrement du polytriméthylène éther glycol (P03G) ou alors proviennent d'un mélange ou d'un copolymère de PO3G et d'au moins l'un parmi le polyéthylène éther glycol (PEG) , le polypropylène éther glycol (PPG) , le polytétraméthylène éther glycol (PTMG) , le polyhexaméthylène éther glycol et les copolymères de tétrahydrofuranne (THF) et de 3-alkyl tétrahydrofuranne (3MeTHF) ; comme produit imper-respirant ou comme additif conférant des propriétés d' imper-respirabilité à des polymères thermoplastiques pour constituer une membrane de diffusion sélective en fonction de la nature du gaz ; comme additif à du polyamide 6, du polyamide 6.6 ou du copolyamide sur base 6/6.6 destiné à être transformé en un film pour améliorer les propriétés mécaniques et/ou l'aptitude à la transformation dudit polyamide.PA represents a polyamide block; PE represents a polyether block, and n represents the number of units -PA-PE- of said copolymer, and in which said blocks come either entirely from polytrimethylene ether glycol (PO 3 G) or else come from a mixture or a copolymer of PO3G and at least one of polyethylene ether glycol (PEG), polypropylene ether glycol (PPG), polytetramethylene ether glycol (PTMG), polyhexamethylene ether glycol and copolymers of tetrahydrofuran (THF) and 3- alkyl tetrahydrofuran (3MeTHF); as breathable product or as an additive imparting breathability properties to thermoplastic polymers to form a selective diffusion membrane depending on the nature of the gas; as an additive to polyamide 6, polyamide 6.6 or copolyamide based on 6 / 6.6 to be converted into a film to improve the mechanical properties and / or processability of said polyamide.
Selon un mode de réalisation, lesdits blocs PE ont une masse moléculaire < 800.According to one embodiment, said PE blocks have a molecular weight <800.
Selon un mode de réalisation, lesdits blocs PE ont une masse moléculaire d'au moins 250.According to one embodiment, said PE blocks have a molecular weight of at least 250.
Selon un mode de réalisation, lesdits blocs PE ont une masse moléculaire comprise entre 250 et 650.
Selon un mode de réalisation, le copolymère est caractérisé par le fait qu'au moins 10%, de préférence au moins 20%, encore plus préférentiellement au moins 30%, avantageusement au moins 50%, encore plus avantageusement au moins 75% et, de façon davantage préférée, 85 à 100% en poids des blocs PE proviennent du polytriméthylène éther glycol (% en poids par rapport au poids total desdits blocs PE) .According to one embodiment, said PE blocks have a molecular mass of between 250 and 650. According to one embodiment, the copolymer is characterized in that at least 10%, preferably at least 20%, even more preferably at least 30%, advantageously at least 50%, still more advantageously at least 75% and, more preferably, 85 to 100% by weight of the PE blocks are from polytrimethylene ether glycol (% by weight based on the total weight of said PE blocks).
Le pourcentage en poids de blocs PA par rapport au poids total dusit copolymère est notamment d'au moins 10%, de façon davantage préférée, d'au moins 15%, et va de préférence jusqu'à 90%, de façon plus préférée entre 40 et 60%.The percentage by weight of PA blocks relative to the total weight of said copolymer is in particular at least 10%, more preferably at least 15%, and preferably up to 90%, more preferably between 40 and 60%.
Les blocs PA ont notamment une masse moléculaire moyenne en nombre d'au moins 300, de préférence d'au moins 600, et allant de préférence jusqu'à 10,000, de façon plus préférée jusqu'à 5000 et de façon encore plus préférée jusqu'à 3000. n va de 1, étant en particulier d'au moins 5, de façon davantage préférée d'au moins 6, et allant jusqu'à une moyenne de 60, de façon préférée jusqu'à une moyenne de 30, de façon davantage préférée jusqu'à une moyenne de 25.The PA blocks have in particular a number-average molecular mass of at least 300, preferably at least 600, and preferably ranging up to 10,000, more preferably up to 5000, and even more preferably up to at 3000. n is 1, being in particular at least 5, more preferably at least 6, and up to an average of 60, preferably up to an average of 30, so more preferred up to an average of 25.
Les blocs PA sont notamment à extrémités carboxyliques de telle sorte que les liaisons entre les blocs PA et PE sont des liaisons ester.The PA blocks are in particular carboxylic ends so that the bonds between the PA and PE blocks are ester bonds.
Les blocs PA à extrémités carboxyliques peuvent être le produit de condensation d'un lactame, en particulier d'un lactame en C4-Ci4, d'un amino acide en particulier d'un amino acide en C4-Ci4 ou d'une combinaison des deux, avec un acide dicarboxylique, en particulier d'un acide dicarboxylique en C4-C2o •The PA blocks having carboxylic end groups may be the condensation product of a lactam, in particular a lactam C 4 -C 4, an amino acid, in particular an amino acid, C 4 -C 4 or a combination of both with a dicarboxylic acid, in particular a C 4 -C 20 dicarboxylic acid;
A titre d'exemples de lactames, on peut citer le caprolactame, l 'oenantholactame et le lauryllactame .Examples of lactams include caprolactam, oenantholactam and lauryllactam.
A titre d'exemples d'amino acides, on peut citer les acides aminocaproïque, amino-7-heptanoïque, amino-11- undécanoïque et amino-12-dodécanoïque .
A titre d'exemples d'acides dicarboxyliques, on peut citer l'acide 1, 4-cyclohexyldicarboxylique, les acides butanedioïque, adipique, azélaïque, subérique, sébacique, dodécanedicarboxylique, et les acides téréphtalique et isophtalique, mais aussi les acides gras dimérisés.Examples of amino acids that may be mentioned include aminocaproic acid, amino-7-heptanoic acid, amino-11-undecanoic acid and amino-12-dodecanoic acid. Examples of dicarboxylic acids that may be mentioned include 1,4-cyclohexyldicarboxylic acid, butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic and terephthalic and isophthalic acids, but also dimerized fatty acids.
Les blocs PA à extrémités carboxyliques peuvent aussi être le produit de condensation d'un acide dicarboxylique tel qu'un acide alkyl en C4-C20- dicarboxylique et d'une diamine, en particulier d'une diamine en C2-C20-The carboxyl-terminated PA blocks may also be the condensation product of a dicarboxylic acid such as a C 4 -C 20 alkyl dicarboxylic acid and a diamine, especially a C 2 -C 20 diamine.
Des exemples d'acides dicarboxyliques ont été indiqués ci-dessus.Examples of dicarboxylic acids have been indicated above.
A titre d'exemples de diamines, on peut citer 1 'hexaméthylènediamine, la dodécaméthylènediamine, la triméthylhexaméthylène diamine, les isomères des bis- (4- aminocyclohexyl ) -méthane (BACM), bis- (3-méthyl-4- aminocyclohexyl ) méthane (BMACM), et 2-2-bis- (3-méthyl-4- aminocyclohexyl) -propane (BMACP), et para-amino-di-cyclo- hexyl-méthane (PACM), et 1 ' isophoronediamine (IPDA), la 2 , 6-bis- (aminométhyl ) -norbornane (BAMN) et la pipérazine.As examples of diamines, mention may be made of hexamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, isomers of bis (4-aminocyclohexyl) methane (BACM), bis (3-methyl-4-aminocyclohexyl) methane (BMACM), and 2-2-bis- (3-methyl-4-aminocyclohexyl) -propane (BMACP), and para-amino-di-cyclohexyl-methane (PACM), and isophoronediamine (IPDA), 2,6-bis (aminomethyl) norbornane (BAMN) and piperazine.
En particulier, les blocs PA peuvent être choisis parmi les blocs PA 6, PA 11, PA 12, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 6.14, PA 6.18, PA Pip.10 et PA 9.6.In particular, the PA blocks can be chosen from the blocks PA 6, PA 11, PA 12, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 6.14, PA 6.18, PA Pip.10 and PA 9.6.
Les blocs PE proviennent soit entièrement du polytriméthylène éther glycol (PO3G) ou alors ils proviennent également avantageusement de PO3G et d'au moins l'un parmi le polyéthylène éther glycol (PEG), le polypropylène éther glycol (PPG) , le polytétraméthylène éther glycol (PTMG) , le polyhexaméthylène éther glycol et les copolymères de tétrahydrofuranne (THF) et de 3-alkyl tétrahydrofuranne (3MeTHF) . On peut également envisager un bloc PE de type « copolyéthers » contenant un enchaînement de blocs PE des types cités ci-dessus. Les fins de chaînes des copolyéthers peuvent être diOH, diNH2, diisocyanate ou diacide suivant leur procédé de synthèse.The PE blocks come either entirely from polytrimethylene ether glycol (PO3G) or they also advantageously come from PO3G and from at least one of polyethylene ether glycol (PEG), polypropylene ether glycol (PPG), polytetramethylene ether glycol (PTMG), polyhexamethylene ether glycol and copolymers of tetrahydrofuran (THF) and 3-alkyl tetrahydrofuran (3MeTHF). It is also possible to envisage a PE block of "copolyether" type containing a series of PE blocks of the types mentioned above. The chain ends of the copolyethers can be diOH, diNH 2, diisocyanate or diacid according to their synthesis process.
Les polyéther glycols en plus du PO3G dans le bloc PE ont une masse molaire moyenne telle que le bloc PE
les contenant a une masse molaire moyenne d'au moins environ 800, plus préférablement d'au moins environ 1000, et de manière préférentielle d'au moins environ 1500. De plus, de préférence au moins environ 50 % en poids, plus préférablement au moins 75 % en poids, et de manière plus préférentielle environ 85 à 100 % en poids, du polyéther glycol utilisé pour former le bloc PE est du PO3G.The polyether glycols in addition to PO3G in the PE block have an average molecular weight such that the PE block the containers have an average molecular weight of at least about 800, more preferably at least about 1000, and preferably at least about 1500. Also, preferably at least about 50% by weight, more preferably at least about less than 75% by weight, and more preferably about 85 to 100% by weight, of the polyether glycol used to form the PE block is PO3G.
La présente invention porte plus précisément sur l'utilisation d'un copolymère de formule (I) tel que défini ci-dessus comme produit antistatique ou comme additif conférant des propriétés antistatiques à des polymères thermoplastiques tels que les polyamides ou à des élastomères .The present invention relates more specifically to the use of a copolymer of formula (I) as defined above as an antistatic product or as an additive imparting antistatic properties to thermoplastic polymers such as polyamides or elastomers.
La présente invention porte aussi plus pariculièrement sur l'utilisation d'un copolymère de formule (I) tel que défini ci-dessus comme produit imper- respirant ou comme additif conférant des propriétés d ' imper-respirabilité à des polymères thermoplastiques tels que les polyamides ou à des élastomères.The present invention also relates more particularly to the use of a copolymer of formula (I) as defined above as a breathable product or as an additive imparting properties of breathability to thermoplastic polymers such as polyamides. or elastomers.
La présente invention porte aussi plus particulièrement sur l'utilisation d'un copolymère de formule (I) tel que défini ci-dessus pour constituer une membrane de diffusion sélective en fonction de la nature du gaz .The present invention also relates more particularly to the use of a copolymer of formula (I) as defined above to form a selective diffusion membrane depending on the nature of the gas.
En particulier, le copolymère de formule (I) peut être utilisé comme additif à du polyamide 6, du polyamide 6.6 ou un copolyamide sur base 6 / 6.6 destiné à être transformé en un film pour améliorer les propriétés mécaniques et/ou l'aptitude à la transformation du polyamide .In particular, the copolymer of formula (I) can be used as an additive to polyamide 6, polyamide 6.6 or a copolyamide based on 6 / 6.6 to be converted into a film to improve the mechanical properties and / or the the transformation of polyamide.
S 'agissant de leur préparation, les copolymères de l'invention peuvent être préparés par tout moyen permettant d'accrocher les blocs polyamide et les blocs polyéther. En pratique, on utilise essentiellement deux procédés l'un dit en deux étapes, l'autre en une étape. Dans le procédé en deux étapes on fabrique d'abord les blocs polyamide puis dans une deuxième étape, on accroche
les blocs polyamide et les blocs polyéther. Dans le procédé en une étape, on mélange les précurseurs de polyamide, le régulateur de chaînes (ou l'acide dicarboxylique ou la diamine en excès stoèchiométrique) et le polyéther ; on obtient alors un polymère ayant essentiellement des blocs polyéther, des blocs polyamide de longueur très variable, mais aussi les différents réactifs ayant réagi de façon aléatoire qui sont répartis de façon aléatoire (statistique) le long de la chaîne polymère.With regard to their preparation, the copolymers of the invention may be prepared by any means for hanging the polyamide blocks and the polyether blocks. In practice, essentially two methods are used, one said in two steps, the other in one step. In the two-step process, the polyamide blocks are first manufactured and then, in a second step, polyamide blocks and polyether blocks. In the one-step process, the polyamide precursors, the chain regulator (or the dicarboxylic acid or stoichiometric excess diamine) and the polyether are mixed; a polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reagents reacted in a random manner which are distributed randomly (statistically) along the polymer chain.
Que ce soit en une ou deux étapes, il est avantageux d'opérer en présence d'un catalyseur. On peut utiliser les catalyseurs décrits dans les brevets US 4 331 786, US 4 115 475, US 4 195 015, US 4 839 441, US 4 864 014, US 4 230 838 et US 4 332 920.Whether in one or two stages, it is advantageous to operate in the presence of a catalyst. Catalysts described in US Pat. Nos. 4,331,786, 4,155,475, 4,195,155, 4,839,441, 4,884,014, 4,230,838 and 4,332,920 can be used.
On peut également utiliser un procédé pour lequel on commence par transformer le polyéther diol en polyéther diamine, diacide ou diisocyanate pour le faire réagir ensuite avec le bloc PA diacide ou diamine.
It is also possible to use a process for which the polyether diol is first converted into polyether diamine, diacid or diisocyanate, then reacted with the diacid or diamine PA block.
Claims
REVENDICATIONS
1 - Utilisation d'un copolymère comprenant des blocs polyamide et des blocs polyéther de formule générale1 - Use of a Copolymer Comprising Polyamide Blocks and Polyether Blocks of General Formula
( \J±)) — ΓιPJrΛA — PJrFIL iJ n—(\ J ±)) - ΓιPJrΛA - PJrFIL iJ n -
dans laquellein which
PA représente un bloc polyamide ; PE représente un bloc polyéther, etPA represents a polyamide block; PE represents a polyether block, and
- n représente le nombre d'unités -PA-PE- dudit copolymère, et dans laquelle lesdits blocs proviennent soit entièrement du polytriméthylène éther glycol (PO3G) ou alors proviennent d'un mélange ou d'un copolymère de PO3G et d'au moins l'un parmi le polyéthylène éther glycol (PEG) , le polypropylène éther glycol (PPG) , le polytétraméthylène éther glycol (PTMG) , le polyhexaméthylène éther glycol et les copolymères de tétrahydrofuranne (THF) et de 3-alkyl tétrahydrofuranne (3MeTHF) ; comme produit imper-respirant ou comme additif conférant des propriétés d' imper-respirabilité à des polymères thermoplastiques pour constituer une membrane de diffusion sélective en fonction de la nature du gaz ; comme additif à du polyamide 6, du polyamide 6.6 ou du copolyamide sur base 6/6.6 destiné à être transformé en un film pour améliorer les propriétés mécaniques et/ou l'aptitude à la transformation dudit polyamide.n represents the number of units -PA-PE- of said copolymer, and in which said blocks come either entirely from polytrimethylene ether glycol (PO3G) or else come from a mixture or a copolymer of PO3G and at least one of polyethylene ether glycol (PEG), polypropylene ether glycol (PPG), polytetramethylene ether glycol (PTMG), polyhexamethylene ether glycol and copolymers of tetrahydrofuran (THF) and 3-alkyl tetrahydrofuran (3MeTHF); as breathable product or as an additive imparting breathability properties to thermoplastic polymers to form a selective diffusion membrane depending on the nature of the gas; as an additive to polyamide 6, polyamide 6.6 or copolyamide based on 6 / 6.6 to be converted into a film to improve the mechanical properties and / or processability of said polyamide.
2 - Utilisation selon la revendication 1, caractérisé en ce que lesdits blocs PE ont une masse moléculaire < 800.
3 - Utilisation du copolymère selon la revendication 2, caractérisée en ce que la masse moléculaire desdits blocs PE est d'au moins 250.2 - Use according to claim 1, characterized in that said PE blocks have a molecular weight <800. 3 - Use of the copolymer according to claim 2, characterized in that the molecular weight of said PE blocks is at least 250.
4 - Utilisation du copolymère selon l'une des revendications précédentes, caractérisée en ce que la masse moléculaire desdits blocs PE est comprise entre 250 et 650.4 - Use of the copolymer according to one of the preceding claims, characterized in that the molecular weight of said PE blocks is between 250 and 650.
5 - Utilisation du copolymère selon l'une des revendications précédentes, caractérisée par le fait qu'au moins 10%, de préférence au moins 20%, encore plus préférentiellement au moins 30%, avantageusement au moins 50%, encore plus avantageusement au moins 75% et, de façon davantage préférée, 85 à 100% en poids des blocs PE proviennent du polytriméthylène éther glycol (% en poids par rapport au poids total desdits blocs PE) .5 - Use of the copolymer according to one of the preceding claims, characterized in that at least 10%, preferably at least 20%, even more preferably at least 30%, advantageously at least 50%, even more advantageously at least 75% and, more preferably, 85 to 100% by weight of the PE blocks are derived from polytrimethylene ether glycol (% by weight based on the total weight of said PE blocks).
6 - Utilisation selon l'une des revendications précédentes, caractérisée par le fait que le pourcentage en poids de blocs PA par rapport au poids total dudit copolymère est d'au moins 10%, de façon davantage préférée, d'au moins 15%, et va de préférence jusqu'à 90%, de façon plus préférée entre 40% et 60%.6 - Use according to one of the preceding claims, characterized in that the weight percentage of PA blocks relative to the total weight of said copolymer is at least 10%, more preferably at least 15%, and is preferably up to 90%, more preferably between 40% and 60%.
7 - Utilisation selon l'une des revendications précédentes, caractérisée par le fait que les blocs PA ont une masse moléculaire moyenne en nombre d'au moins 300, de préférence d'au moins 600, et allant de préférence jusqu'à 10000, de façon plus préférée jusqu'à 5000, et de façon encore plus préférée jusqu'à 3000.7 - Use according to one of the preceding claims, characterized in that the PA blocks have a number average molecular weight of at least 300, preferably at least 600, and preferably up to 10000, of more preferred way up to 5000, and even more preferably up to 3000.
8 - Utilisation selon l'une des revendications précédentes, caractérisée par le fait que les blocs PE ont une masse moléculaire moyenne en nombre d'au moins 250, de façon plus préférée d'au moins 1000, et de façon encore plus préférée, d'au moins 1500, et allant, de préférence, jusqu'à 5000, de façon plus préférée jusqu'à 4000, et de façon encore plus préférée jusqu'à 2000.8 - Use according to one of the preceding claims, characterized in that the PE blocks have a number average molecular weight of at least 250, more preferably at least 1000, and even more preferably, at least 1500, and preferably up to 5000, more preferably up to 4000, and even more preferably up to 2000.
9 - Utilisation selon l'une des revendications précédentes, caractérisée par le fait que n va de 1, étant
en particulier d'au moins 5, de façon davantage préférée d'au moins 6, et allant jusqu'à une moyenne de 60, de façon préférée jusqu'à une moyenne de 30, de façon davantage préférée jusqu'à une moyenne de 25.9 - Use according to one of the preceding claims, characterized in that n ranges from 1, being in particular at least 5, more preferably at least 6, and up to an average of 60, more preferably up to an average of 30, more preferably up to an average of 25. .
10 - Utilisation selon l'une des revendications précédentes, caractérisée par le fait que les blocs PA sont à extrémités carboxyliques de telle sorte que les liaisons entre les blocs PA et PE sont des liaisons ester.10 - Use according to one of the preceding claims, characterized in that the PA blocks are carboxylic ends so that the bonds between PA and PE blocks are ester bonds.
11 - Utilisation selon la revendication 10, caractérisée par le fait que les blocs PA à extrémités carboxyliques sont le produit de condensation d'un lactame, en particulier d'un lactame en C4-Ci4, d'un amino acide en en particulier d'un amino acide en C4-Ci4 ou d'une combinaison des deux, avec un acide dicarboxylique, en particulier d'un acide dicarboxylique en C4-C20.11 - Use according to claim 10, characterized in that the PA blocks having carboxylic end groups are the condensation product of a lactam, in particular a lactam C 4 -C 4, an amino acid, in particular of a C 4 -C 4 amino acid or a combination of both with a dicarboxylic acid, in particular a C 4 -C 20 dicarboxylic acid.
12 - Utilisation selon la revendication 10, caractérisée par le fait que les blocs PA à extrémités carboxyliques sont le produit de condensation d'un acide dicarboxylique tel qu'un acide alkyl en C4-C2O- dicarboxylique et d'une diamine, en particulier d'une diamine en C2-C2O.12 - Use according to claim 10, characterized in that the PA blocks with carboxylic ends are the condensation product of a dicarboxylic acid such as a C 4 -C 2 O alkyl dicarboxylic acid and a diamine, in particular a C 2 -C 2 O diamine.
13 - Utilisation selon l'une des revendications précédentes, caractérisée par le fait que les blocs PA sont choisis parmi les blocs PA 6, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 6.14, PA 6.18, PA Pip.10 et PA 9.6.
13 - Use according to one of the preceding claims, characterized in that the PA blocks are selected from the blocks PA 6, PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 6.14, PA 6.18, PA Pip.10 and PA 9.6.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0601354A FR2897354A1 (en) | 2006-02-16 | 2006-02-16 | Use of a copolymer e.g. as a breathable-water proof product, an additive conferring breathable-water proof properties on thermoplastic polymers to form a membrane with selective diffusion as a function of the type of gas |
US78435506P | 2006-03-21 | 2006-03-21 | |
PCT/FR2007/050817 WO2007093752A2 (en) | 2006-02-16 | 2007-02-16 | Novel use of a copolymer comprising polyamide blocks and polyether blocks originating at least partially from polytrimethylene ether glycol |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1994077A2 true EP1994077A2 (en) | 2008-11-26 |
Family
ID=36956178
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07731641A Withdrawn EP1994077A2 (en) | 2006-02-16 | 2007-02-16 | Novel use of a copolymer comprising polyamide blocks and polyether blocks originating at least partially from polytrimethylene ether glycol |
Country Status (9)
Country | Link |
---|---|
US (1) | US20090221767A1 (en) |
EP (1) | EP1994077A2 (en) |
JP (1) | JP2009526892A (en) |
KR (1) | KR20080093056A (en) |
CN (1) | CN101426567A (en) |
CA (1) | CA2642439A1 (en) |
FR (1) | FR2897354A1 (en) |
TW (1) | TW200745221A (en) |
WO (1) | WO2007093752A2 (en) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MX342897B (en) | 2009-04-28 | 2016-10-18 | Surmodics Inc | Devices and methods for delivery of bioactive agents. |
US8883284B2 (en) * | 2010-09-03 | 2014-11-11 | Transhield Technology As | Vapor permeable fabric constructs with static or dynamic antimicrobial compositions |
FR2965269B1 (en) * | 2010-09-28 | 2013-10-04 | Arkema France | PEBA-BASED COMPOSITION AND USE THEREOF FOR THE MANUFACTURE OF TRANSPARENT OBJECTS RESISTANT TO HIGH SPEED IMPACT |
FR2969525A1 (en) * | 2010-12-27 | 2012-06-29 | Arkema France | WOOD / POLYMER COMPOSITE WITH IMPROVED THERMAL STABILITY |
US9861727B2 (en) | 2011-05-20 | 2018-01-09 | Surmodics, Inc. | Delivery of hydrophobic active agent particles |
US10213529B2 (en) | 2011-05-20 | 2019-02-26 | Surmodics, Inc. | Delivery of coated hydrophobic active agent particles |
WO2013002602A2 (en) * | 2011-06-30 | 2013-01-03 | 코오롱인더스트리 주식회사 | Film for an inner liner of a tire and method for manufacturing same |
US9399374B2 (en) | 2011-06-30 | 2016-07-26 | Kolon Industries, Inc. | Film for a tire inner liner and preparation method therefor |
US11246963B2 (en) | 2012-11-05 | 2022-02-15 | Surmodics, Inc. | Compositions and methods for delivery of hydrophobic active agents |
WO2014104864A1 (en) * | 2012-12-31 | 2014-07-03 | 코오롱인더스트리 주식회사 | Cross-linked polymer, polymer resin composition, and polymer film |
US20150121888A1 (en) * | 2013-11-05 | 2015-05-07 | General Electric Company | Gas turbine online wash control |
US20170298182A1 (en) * | 2014-09-24 | 2017-10-19 | Bridgestone Corporation | Tire |
FR3037961B1 (en) * | 2015-06-26 | 2019-12-20 | Arkema France | PEBA FOR DIRECT ADHESION ON TPE |
US10898446B2 (en) | 2016-12-20 | 2021-01-26 | Surmodics, Inc. | Delivery of hydrophobic active agents from hydrophilic polyether block amide copolymer surfaces |
US10525406B2 (en) * | 2017-05-30 | 2020-01-07 | Saudi Arabian Oil Company | Polymer blended membranes for sour gas separation |
CN113906007A (en) * | 2019-03-26 | 2022-01-07 | 银杏生物制品公司 | 10-methylene lipid derivatives, preparation method and application thereof |
FR3096683B1 (en) * | 2019-05-27 | 2022-03-04 | Arkema France | self-flaming copolyesteramide |
CN113750804B (en) * | 2021-09-15 | 2022-07-19 | 北京理工大学 | Modified polyisophthaloyl metaphenylene diamine ultrafiltration membrane as well as preparation method and application thereof |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0757801B2 (en) * | 1987-05-30 | 1995-06-21 | ダイセル化学工業株式会社 | New Polyester Ester Amide Block Copolymer |
FR2639644A1 (en) * | 1988-11-25 | 1990-06-01 | Atochem | THERMOPLASTIC ELASTOMERIC FILM PERMEABLE TO WATER VAPOR BASED ON POLYETHERESTERAMIDE, PROCESS FOR PRODUCING THE SAME AND ARTICLES COMPRISING SUCH FILM |
NZ239723A (en) * | 1990-09-18 | 1993-06-25 | Chicopee | Blends comprising a hydrophilic block poly (ether-co-amide) and a hydrophobic polymer |
FR2743566B1 (en) * | 1996-01-16 | 1998-05-07 | Atochem Elf Sa | NOVEL SCENTED RESIN ALLOWING THE REGULAR DIFFUSION OF A COMPLEX SCENTED COMPOSITION |
FR2810988B1 (en) * | 2000-07-03 | 2002-08-16 | Rhodianyl | POLYAMIDE COMPOSITIONS WITH IMPROVED ANTISTATICITY AND HYDROPHILY |
AU6609301A (en) * | 2000-07-06 | 2002-01-14 | Int Coatings Ltd | Antifouling paint |
DE60211281T8 (en) * | 2001-11-27 | 2007-09-06 | Ube Industries, Ltd., Ube | Polyamides with low water absorption capacity |
US6590065B1 (en) * | 2001-12-10 | 2003-07-08 | E. I. Du Pont De Nemours And Company | Polytrimethylene ether ester amide and use thereof |
US6608168B1 (en) * | 2002-08-09 | 2003-08-19 | E. I. Du Pont De Nemours And Company | Polytrimethylene ether esters |
US6979492B2 (en) * | 2002-08-09 | 2005-12-27 | E. I. Du Pont De Nemours And Company | Thermoplastic elastomer comprising poly(trimethylene-ethylene ether) soft segment and polyamide hard segment |
JP2006131890A (en) * | 2004-10-04 | 2006-05-25 | Ube Ind Ltd | Polyamide resin composition and polyamide film |
-
2006
- 2006-02-16 FR FR0601354A patent/FR2897354A1/en not_active Withdrawn
-
2007
- 2007-02-16 CA CA002642439A patent/CA2642439A1/en not_active Abandoned
- 2007-02-16 EP EP07731641A patent/EP1994077A2/en not_active Withdrawn
- 2007-02-16 KR KR1020087019957A patent/KR20080093056A/en not_active Application Discontinuation
- 2007-02-16 CN CNA2007800136601A patent/CN101426567A/en active Pending
- 2007-02-16 TW TW096106369A patent/TW200745221A/en unknown
- 2007-02-16 WO PCT/FR2007/050817 patent/WO2007093752A2/en active Application Filing
- 2007-02-16 JP JP2008554830A patent/JP2009526892A/en not_active Abandoned
- 2007-02-16 US US12/279,578 patent/US20090221767A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO2007093752A2 * |
Also Published As
Publication number | Publication date |
---|---|
TW200745221A (en) | 2007-12-16 |
WO2007093752A3 (en) | 2008-09-12 |
CA2642439A1 (en) | 2007-08-23 |
CN101426567A (en) | 2009-05-06 |
FR2897354A1 (en) | 2007-08-17 |
US20090221767A1 (en) | 2009-09-03 |
KR20080093056A (en) | 2008-10-17 |
JP2009526892A (en) | 2009-07-23 |
WO2007093752A2 (en) | 2007-08-23 |
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