US20100130677A1 - Polyamide-based thermoplastic polymer compositions - Google Patents
Polyamide-based thermoplastic polymer compositions Download PDFInfo
- Publication number
- US20100130677A1 US20100130677A1 US12/527,014 US52701408A US2010130677A1 US 20100130677 A1 US20100130677 A1 US 20100130677A1 US 52701408 A US52701408 A US 52701408A US 2010130677 A1 US2010130677 A1 US 2010130677A1
- Authority
- US
- United States
- Prior art keywords
- polyamide
- ethylene
- polymer composition
- styrene
- copolymers
- 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.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 229920002647 polyamide Polymers 0.000 title claims abstract description 63
- 229920001169 thermoplastic Polymers 0.000 title abstract description 12
- 239000004952 Polyamide Substances 0.000 claims abstract description 56
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- 229920001971 elastomer Polymers 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 26
- 229920001577 copolymer Polymers 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000004609 Impact Modifier Substances 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000806 elastomer Substances 0.000 claims description 18
- 239000005977 Ethylene Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005060 rubber Substances 0.000 claims description 12
- -1 ethylene, propylene, butene Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229920006226 ethylene-acrylic acid Polymers 0.000 claims description 7
- 229920002292 Nylon 6 Polymers 0.000 claims description 6
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 229920002943 EPDM rubber Polymers 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 4
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 4
- 150000003440 styrenes Chemical class 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical class C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000003014 reinforcing effect Effects 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 2
- 241001643597 Evas Species 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 159000000032 aromatic acids Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 claims description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 2
- LKAVYBZHOYOUSX-UHFFFAOYSA-N buta-1,3-diene;2-methylprop-2-enoic acid;styrene Chemical compound C=CC=C.CC(=C)C(O)=O.C=CC1=CC=CC=C1 LKAVYBZHOYOUSX-UHFFFAOYSA-N 0.000 claims description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229920000554 ionomer Polymers 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 2
- 229920001083 polybutene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 239000000039 congener Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 239000003607 modifier Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000035939 shock Effects 0.000 abstract 1
- 239000004416 thermosoftening plastic Substances 0.000 description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical group 0.000 description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920006345 thermoplastic polyamide Polymers 0.000 description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 1
- 229920003317 Fusabond® Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GDAVCKWOYPPSEU-UHFFFAOYSA-N diethyl 4-oxocyclohexane-1,1-dicarboxylate Chemical compound CCOC(=O)C1(C(=O)OCC)CCC(=O)CC1 GDAVCKWOYPPSEU-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XTBMQKZEIICCCS-UHFFFAOYSA-N hexane-1,5-diamine Chemical compound CC(N)CCCCN XTBMQKZEIICCCS-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- PZRHRDRVRGEVNW-UHFFFAOYSA-N milrinone Chemical compound N1C(=O)C(C#N)=CC(C=2C=CN=CC=2)=C1C PZRHRDRVRGEVNW-UHFFFAOYSA-N 0.000 description 1
- 229960003574 milrinone Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
- C08L23/0884—Epoxide-containing esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/18—Homopolymers or copolymers of nitriles
- C08L33/20—Homopolymers or copolymers of acrylonitrile
Definitions
- the present invention relates to a polyamide-based thermoplastic polymer composition that exhibits a good balance between its properties, in particular its mechanical properties, and a high melt flow.
- the invention relates in particular to a composition comprising at least one high-fluidity polyamide and an impact modifier comprising functional groups that react with the polyamide, and to a method for preparing such a composition.
- thermoplastic intended to be formed by techniques such as injection molding, gas injection molding, extrusion and extrusion-blow molding
- stiffness in particular at a relatively high temperature, low post-forming shrinkage
- dimensional stability in particular at a relatively high temperature, low post-forming shrinkage
- capacity for coating by various processes surface appearance and density.
- These properties can be controlled, within certain limits, through the choice of a polymer or through the addition to the polymer of compounds of various natures. In the latter case, the term polymeric compositions is used.
- the choice of a material for a given application is generally guided by the required level of performance with respect to certain properties and by its cost. The aim is always to obtain new materials that can meet a specification in terms of performance and/or cost.
- Polyamide is, for example, a material that is widely used, in particular in the sector of the automobile industry.
- Polyamide is a polymer which is chemically resistant, which is stable at high temperatures and which can be mixed with other types of polymers in order to modify the properties thereof. It is, for example, possible to improve its resilience by adding an elastomeric polymer.
- thermoplastic compositions used should be characterized, in the melting state, by a fluidity and a rheological behavior compatible with the forming processes of interest, such as injection molding.
- these thermoplastic compositions should be sufficiently fluid, when they are molten, for it to be possible to easily and rapidly convey and manipulate them in certain forming devices, such as, for example, injection molding devices.
- thermoplastic compositions that exhibit a high fluidity.
- this increase in fluidity results in a decrease in the mechanical properties of the articles obtained.
- the applicant has developed a polyamide composition that exhibits an increased melt flow and equivalent or superior mechanical properties, in comparison with conventional polyamide compositions, and that makes possible the preparation of articles having an excellent surface appearance, in particular when they comprise a high level of fillers.
- composition comprising at least:
- a polyamide of type 6 or 66 obtained by means of a process of polymerization of the monomers of the polyamide 6 or 66 in the presence, in addition, of monofunctional and/or difunctional compounds comprising carboxylic acid or amine functions; said polyamide having a melt flow index of greater than or equal to 10 g/10 min. according to the ISO1133 standard measured at a temperature of 275° C. with a load of 325 g; and
- the polyamide a) may be a thermoplastic polyamide of type 66, i.e. a polyamide obtained at least from adipic acid and hexamethylenediamine, which may optionally comprise other polyamide monomers.
- polyamide of type 66 is intended in particular to mean a polyamide comprising at least 80 mol %, preferably at least 90 mol % of adipic acid and hexamethylenediamine monomer residues.
- the polyamide a) may be a thermoplastic polyamide of type 6, i.e. a polyamide obtained at least from caprolactam, which may optionally comprise other polyamide monomers.
- polyamide of type 6 is intended in particular to mean a polyamide comprising at least 80 mol %, preferably at least 90 mol % of caprolactam monomer residues.
- the polymerization of the polyamide of the invention is in particular carried out according to the conventional operating conditions for the polymerization of polyamides, continuously or batchwise.
- Such a polymerization process may comprise, briefly:
- the polymer can be cooled advantageously with water, and extruded in the form of rods. These rods are cut up so as to produce granules.
- the polyamide is produced by adding during polymerization, in particular at the beginning of the polymerization, monomers of the polyamides 6 or 66, in the presence, in addition, of difunctional and/or monofunctional compounds.
- difunctional and/or monofunctional compounds have amine or carboxylic acid functions capable of reacting with the polyamide monomers.
- the difunctional compounds may have the same amine or carboxylic acid functionality.
- the difunctional and/or monofunctional compounds used are agents for modifying the chain length of polyamides of type 6 or 66 and make it possible to obtain polyamides having a melt flow index of greater than or equal to 10 g/10 min. according to the ISO1133 standard measured at a temperature of 275° C. with a load of 325 g.
- the polyamide-6 monomers are in particular adipic acid and hexamethylenediamine, or hexamethylenediamine adipate, also called nylon salt or N salt.
- the polyamide-6 monomers are caprolactam or derivatives thereof.
- aliphatic or aromatic monocarboxylic or dicarboxylic acids of any type or aliphatic or aromatic, monoamines or diamines of any type. It is in particular possible to use, as monofunctional compound, n-hexadecylamine, n-octadecylamine and n-dodecylamine, acetic acid, lauric acid, benzylamine and benzoic acid.
- succinic acid terephthalic acid, isophthalic acid, sebacic acid, azelaic acid, dodecanoic acid, fatty acid diamers, di( ⁇ -ethylcarboxy)cyclohexanone, 5-methyl pentamethylenediamine, metaxylylenediamine, isophorone diamine and 1,4-cyclohexanediamine.
- the proportion of acid end groups is different than the proportion of amine end groups, in particular at least twice as many or half as many.
- the amounts of amine and/or acid end groups are determined by potentiometric assays after dissolution of the polyamide. A method is, for example, described in “Encyclopedia of Industrial Chemical Analysis”, volume 17, page 293, 1973.
- the polyamide according to the invention has a melt flow index, according to the ISO1133 standard measured at a temperature of 275° C. with a load of 325 g, of between 10 and 50 g/10 min., more preferably between 20 and 40 g/10 min.
- impact modifier is intended to mean a compound capable of modifying the impact strength of a polyamide composition.
- These impact-modifier compounds comprise functional groups that react with the polyamide a).
- the expression “functional groups that react with the polyamide a)” is intended to mean groups capable of reacting or of interacting chemically with the acid or amine functions of the polyamide, in particular by covalence, ionic or hydrogen interaction or van der Walls bonding. Such reactive groups make it possible to provide good dispersion of the impact modifiers in the polyamide matrix. Good dispersion in the matrix is generally obtained with impact-modifier particles having a size of between 0.1 and 1 ⁇ m.
- the impact modifiers may very well comprise, in themselves, functional groups that react with the polyamide a), for example as regards ethylene acrylic acid (EAA).
- EAA ethylene acrylic acid
- the impact modifiers which are oligomeric or polymeric compounds, comprising at least one of the following monomers, or a mixture thereof: ethylene, propylene, butene, isoprene, diene, acrylate, butadiene, styrene, octene, acrylonitrile, acrylic acid, methacrylic acid, vinyl acetate, vinyl esters such as acrylic and methacrylic esters, and glycidyl methacrylate.
- the compounds according to the invention may also comprise, in addition, monomers other than those mentioned above.
- the base of the impact-modifier compound can be chosen from the group comprising: polyethylenes, polypropylenes, polybutenes, polyisoprenes, ethylene-propylene rubbers (EPRs), ethylene-propylene-diene rubbers (EPDMs), ethylene butene rubbers, ethylene acrylate rubbers, butadiene styrene rubbers, butadiene acrylate rubbers, ethylene octene rubbers, butadiene acrylonitrile rubbers, ethylene acrylic acids (EAAs), ethylene vinyl acetate (EVAs), ethylene acrylic esters (EEAs), acrylonitrile-butadiene-styrene (ABS) copolymers, styrene-ethylene-butadiene-styrene (SEBS) block copolymers, styrene-butadiene-styrene (SBS) copolymers, core
- these impact modifiers may also comprise, generally grafted or copolymerized, functional groups that react with the polyamide a), such as, in particular, functional groups as follows: acids, such as carboxylic acids, salified acids, esters, in particular acrylates and methacrylates, ionomers, glycidyl groups, in particular epoxy groups, glycidyl esters, anhydrides, in particular maleic anhydrides, maleimides, or mixtures thereof.
- acids such as carboxylic acids, salified acids, esters, in particular acrylates and methacrylates, ionomers, glycidyl groups, in particular epoxy groups, glycidyl esters, anhydrides, in particular maleic anhydrides, maleimides, or mixtures thereof.
- Such functional groups on the elastomers are, for example, obtained by using a comonomer during the preparation of the elastomer.
- impact modifiers comprising functional groups that react with the polyamide a
- the proportion by weight of the elastomers b) of the invention in the total composition is in particular between 0.1% and 50%, preferably between 0.1% and 20%, in particular between 0.1% and 10%, in particular the values 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 or any ranges composed of said values, in particular between 1% and 6%.
- reinforcing and/or bulking filler preferably chosen from the group comprising fibrous fillers such as glass fibers, inorganic fillers such as clays, kaolin, or reinforced nanoparticles or nanoparticles made of thermosetting material, and powder fillers such as talc.
- the degree of incorporation of reinforcing and/or bulking filler is in accordance with the standards in the composite material field. It may, for example, be a degree of filler of from 1% to 50% by weight, relative to the total weight of the composition.
- composition may comprise, in addition to the modified polyamide of the invention, one or more other polymers, preferably polyamides or copolyamides.
- composition according to the invention may also comprise additives normally used for the production of polyamide compositions.
- additives normally used for the production of polyamide compositions may also comprise additives normally used for the production of polyamide compositions.
- lubricants flame retardants, plasticizers, nucleating agents, catalysts, agents for improving impact strength, such as optionally grafted elastomers, light and/or heat stabilizers, antioxidants, antistatics, colorants, mattifying agents, molding aids or other conventional additives.
- fillers and additives can be added to the modified polyamide by standard means suited to each filler or additive, such as, for example, during melt blending or polymerization.
- thermoplastic compositions are generally obtained by mixing the various compounds that go to make up the composition, the thermoplastic compounds being in molten form. The process is carried out at more or less high temperature, and at more or less high shear force depending on the nature of the various compounds.
- the compounds can be introduced simultaneously or successively.
- An extrusion device in which the material is heated, subjected to a shear force and conveyed along, is generally used. Such devices are entirely known to those skilled in the art.
- all the compounds are melt blended during a single operation, for example during an extrusion operation. It is, for example, possible to blend granules of the polymeric materials, and to introduce them into the extrusion device in order to melt them and to subject them to a more or less large shear stress.
- pre-blends which may or may not be melt pre-blends, of some of the compounds before preparation of the final composition.
- the composition according to the invention when it is prepared using an extrusion device, is preferably conditioned in the form of granules.
- the granules are intended to be formed by means of processes involving melting so as to obtain articles.
- the articles are thus made up of the composition.
- the modified polyamide is extruded in the form of rods, for example in a twin-extrusion device, and said rods are then cut into granules.
- the molded components are then prepared by melting the granules produced above and feeding the molten composition into injection molding devices.
- compositions according to the invention is particularly advantageous in the context of the electrical industry, in particular for the molding of components of large sizes or with a complex geometry.
- compositions are prepared by melt blending, using a Werner and Pfleiderer ZSK twin-screw extruder, the polyamides, 5% by weight of elastomers, 30% by weight of glass fibers, and 1.3% by weight of additives.
- the extrusion conditions are the following: temperature: between 240 and 280° C., rotation speed: between 200 and 300 rpm, flow rate between 25 and 60 kg/hour.
- the spiral test makes it possible to quantify the fluidity of the compositions by melting the granules and injecting them into a spiral-shaped mold with a semicircular cross section of thickness 2 mm and of width 4 cm, in a BM-Biraghi 85T press at a barrel temperature of 275° C. and a mold temperature of 80° C. and with a maximum injection pressure of 130 bar, which corresponds to an injection time of approximately 0.4 seconds (the result is expressed as length of mold correctly filled by the composition).
- compositions obtained exhibit excellent compatibilization between the polyamide of the invention and the grafted elastomers, thereby resulting in the obtaining of articles having an excellent balance between mechanical properties and melt flow. It is, moreover, observed that the articles of Examples 1-8 exhibit a good surface appearance.
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Abstract
Polyamide-based thermoplastic polymer compositions that exhibit a good balance among the properties thereof, in particular their mechanical properties, and a high fluidity in the molten state; such compositions contain at least one high-fluidity polyamide and a shock modification agent having functional groups that react with the polyamide.
Description
- The present invention relates to a polyamide-based thermoplastic polymer composition that exhibits a good balance between its properties, in particular its mechanical properties, and a high melt flow. The invention relates in particular to a composition comprising at least one high-fluidity polyamide and an impact modifier comprising functional groups that react with the polyamide, and to a method for preparing such a composition.
- Among the properties that it is often desired to control in the case of a thermoplastic intended to be formed by techniques such as injection molding, gas injection molding, extrusion and extrusion-blow molding, mention may be made of stiffness, impact strength, dimensional stability, in particular at a relatively high temperature, low post-forming shrinkage, a capacity for coating by various processes, surface appearance and density. These properties can be controlled, within certain limits, through the choice of a polymer or through the addition to the polymer of compounds of various natures. In the latter case, the term polymeric compositions is used. The choice of a material for a given application is generally guided by the required level of performance with respect to certain properties and by its cost. The aim is always to obtain new materials that can meet a specification in terms of performance and/or cost. Polyamide is, for example, a material that is widely used, in particular in the sector of the automobile industry.
- Polyamide is a polymer which is chemically resistant, which is stable at high temperatures and which can be mixed with other types of polymers in order to modify the properties thereof. It is, for example, possible to improve its resilience by adding an elastomeric polymer.
- There are at least three major properties that it is desired to obtain for these polyamide-based compositions, in particular when they are used in these conversion processes.
- The first of these properties lies in the fact that these thermoplastic compositions used should be characterized, in the melting state, by a fluidity and a rheological behavior compatible with the forming processes of interest, such as injection molding. Specifically, these thermoplastic compositions should be sufficiently fluid, when they are molten, for it to be possible to easily and rapidly convey and manipulate them in certain forming devices, such as, for example, injection molding devices.
- It is also sought to increase the mechanical properties of these compositions. These mechanical properties are in particular the impact strength, the flexural or tensile modulus, the flexural strength or tensile strength, inter alia. Reinforcing fillers, such as glass fibers, are generally used to this effect.
- Finally, in the case of components molded from these thermoplastic compositions, a clean and uniform surface appearance is desired. This constraint becomes a problem which is difficult to solve, particularly when a thermoplastic composition with a high load of glass fibers is used, these glass fibers detrimentally affecting the surface appearance of the molded components. It is known practice, in order to obtain an acceptable surface appearance, to use thermoplastic compositions that exhibit a high fluidity. However, this increase in fluidity results in a decrease in the mechanical properties of the articles obtained.
- The result is thus that it is difficult to obtain these various properties for the same polyamide-based thermoplastic composition.
- The applicant has developed a polyamide composition that exhibits an increased melt flow and equivalent or superior mechanical properties, in comparison with conventional polyamide compositions, and that makes possible the preparation of articles having an excellent surface appearance, in particular when they comprise a high level of fillers.
- The subject of the invention is thus a composition comprising at least:
- a) a polyamide of type 6 or 66 obtained by means of a process of polymerization of the monomers of the polyamide 6 or 66 in the presence, in addition, of monofunctional and/or difunctional compounds comprising carboxylic acid or amine functions; said polyamide having a melt flow index of greater than or equal to 10 g/10 min. according to the ISO1133 standard measured at a temperature of 275° C. with a load of 325 g; and
- b) an impact modifier comprising functional groups that react with the polyamide a).
- The polyamide a) may be a thermoplastic polyamide of type 66, i.e. a polyamide obtained at least from adipic acid and hexamethylenediamine, which may optionally comprise other polyamide monomers.
- The term “polyamide of type 66” is intended in particular to mean a polyamide comprising at least 80 mol %, preferably at least 90 mol % of adipic acid and hexamethylenediamine monomer residues.
- The polyamide a) may be a thermoplastic polyamide of type 6, i.e. a polyamide obtained at least from caprolactam, which may optionally comprise other polyamide monomers.
- The term “polyamide of type 6” is intended in particular to mean a polyamide comprising at least 80 mol %, preferably at least 90 mol % of caprolactam monomer residues.
- Preferably, the polyamide according to the invention has a molecular weight Mn of between 3000 and 25000 g/mol, more preferably between 5000 and 15000. It may have a polydispersity index (D=Mw/Mn) of less than or equal to 2.
- The polymerization of the polyamide of the invention is in particular carried out according to the conventional operating conditions for the polymerization of polyamides, continuously or batchwise.
- Such a polymerization process may comprise, briefly:
-
- heating the mixture of monomers and water, with stirring and under pressure; and
- maintaining the mixture at this temperature for a given period of time, followed by decompression and maintaining, for a given period of time, at a temperature above the melting point of the mixture, in particular under nitrogen or under vacuum, so as to thus continue the polymerization by removal of the water formed.
- At the end of polymerization, the polymer can be cooled advantageously with water, and extruded in the form of rods. These rods are cut up so as to produce granules.
- According to the invention, the polyamide is produced by adding during polymerization, in particular at the beginning of the polymerization, monomers of the polyamides 6 or 66, in the presence, in addition, of difunctional and/or monofunctional compounds. These difunctional and/or monofunctional compounds have amine or carboxylic acid functions capable of reacting with the polyamide monomers. The difunctional compounds may have the same amine or carboxylic acid functionality.
- The difunctional and/or monofunctional compounds used are agents for modifying the chain length of polyamides of type 6 or 66 and make it possible to obtain polyamides having a melt flow index of greater than or equal to 10 g/10 min. according to the ISO1133 standard measured at a temperature of 275° C. with a load of 325 g.
- The polyamide-6 monomers are in particular adipic acid and hexamethylenediamine, or hexamethylenediamine adipate, also called nylon salt or N salt. The polyamide-6 monomers are caprolactam or derivatives thereof.
- It is possible to use, at the beginning, during or at the end of polymerization, aliphatic or aromatic, monocarboxylic or dicarboxylic acids of any type or aliphatic or aromatic, monoamines or diamines of any type. It is in particular possible to use, as monofunctional compound, n-hexadecylamine, n-octadecylamine and n-dodecylamine, acetic acid, lauric acid, benzylamine and benzoic acid. It is in particular possible to use, as difunctional compound, succinic acid, terephthalic acid, isophthalic acid, sebacic acid, azelaic acid, dodecanoic acid, fatty acid diamers, di(β-ethylcarboxy)cyclohexanone, 5-methyl pentamethylenediamine, metaxylylenediamine, isophorone diamine and 1,4-cyclohexanediamine.
- It is also possible to use an excess of adipic acid or an excess of hexamethylenediamine for the production of a polyamide of type 66 that exhibits a high melt flow.
- Preferably, the proportion of acid end groups is different than the proportion of amine end groups, in particular at least twice as many or half as many. The amounts of amine and/or acid end groups are determined by potentiometric assays after dissolution of the polyamide. A method is, for example, described in “Encyclopedia of Industrial Chemical Analysis”, volume 17, page 293, 1973.
- Preferably, the polyamide according to the invention has a melt flow index, according to the ISO1133 standard measured at a temperature of 275° C. with a load of 325 g, of between 10 and 50 g/10 min., more preferably between 20 and 40 g/10 min.
- According to the invention, the term “impact modifier” is intended to mean a compound capable of modifying the impact strength of a polyamide composition. These impact-modifier compounds comprise functional groups that react with the polyamide a).
- According to the invention, the expression “functional groups that react with the polyamide a)” is intended to mean groups capable of reacting or of interacting chemically with the acid or amine functions of the polyamide, in particular by covalence, ionic or hydrogen interaction or van der Walls bonding. Such reactive groups make it possible to provide good dispersion of the impact modifiers in the polyamide matrix. Good dispersion in the matrix is generally obtained with impact-modifier particles having a size of between 0.1 and 1 μm.
- The impact modifiers may very well comprise, in themselves, functional groups that react with the polyamide a), for example as regards ethylene acrylic acid (EAA).
- It is also possible to attach thereto functional groups that react with the polyamide a), generally by grafting or copolymerization, for example for ethylene-propylene-diene (EPDM) grafted with maleic anhydride.
- According to the invention, use may be made of the impact modifiers, which are oligomeric or polymeric compounds, comprising at least one of the following monomers, or a mixture thereof: ethylene, propylene, butene, isoprene, diene, acrylate, butadiene, styrene, octene, acrylonitrile, acrylic acid, methacrylic acid, vinyl acetate, vinyl esters such as acrylic and methacrylic esters, and glycidyl methacrylate.
- The compounds according to the invention may also comprise, in addition, monomers other than those mentioned above.
- The base of the impact-modifier compound, optionally referred to as elastomeric base, can be chosen from the group comprising: polyethylenes, polypropylenes, polybutenes, polyisoprenes, ethylene-propylene rubbers (EPRs), ethylene-propylene-diene rubbers (EPDMs), ethylene butene rubbers, ethylene acrylate rubbers, butadiene styrene rubbers, butadiene acrylate rubbers, ethylene octene rubbers, butadiene acrylonitrile rubbers, ethylene acrylic acids (EAAs), ethylene vinyl acetate (EVAs), ethylene acrylic esters (EEAs), acrylonitrile-butadiene-styrene (ABS) copolymers, styrene-ethylene-butadiene-styrene (SEBS) block copolymers, styrene-butadiene-styrene (SBS) copolymers, core-shell elastomers of methacrylate-butadiene-styrene (MBS) type, or blends of at least two elastomers listed above.
- In addition to the groups listed above, these impact modifiers may also comprise, generally grafted or copolymerized, functional groups that react with the polyamide a), such as, in particular, functional groups as follows: acids, such as carboxylic acids, salified acids, esters, in particular acrylates and methacrylates, ionomers, glycidyl groups, in particular epoxy groups, glycidyl esters, anhydrides, in particular maleic anhydrides, maleimides, or mixtures thereof.
- Such functional groups on the elastomers are, for example, obtained by using a comonomer during the preparation of the elastomer.
- As impact modifiers comprising functional groups that react with the polyamide a), mention may in particular be made of ethylene/acrylic ester/glycidyl methacrylate terpolymers, ethylene/butyl ester acrylate copolymers, ethylene/n-butyl acrylate/glycidyl methacrylate copolymers, ethylene/maleic anhydride copolymers, maleic anhydride-grafted styrene/maleimide copolymers, copolymers of styrene/ethylene/butylene/styrene modified with maleic anhydride, maleic anhydride-grafted styrene/acrylonitrile copolymers, maleic anhydride-grafted acrylonitrile/butadiene/styrene copolymers, and hydrogenated versions thereof.
- The proportion by weight of the elastomers b) of the invention in the total composition is in particular between 0.1% and 50%, preferably between 0.1% and 20%, in particular between 0.1% and 10%, in particular the values 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 or any ranges composed of said values, in particular between 1% and 6%.
- In order to improve the mechanical properties of the composition according to the invention, it may be advantageous to add thereto at least one reinforcing and/or bulking filler preferably chosen from the group comprising fibrous fillers such as glass fibers, inorganic fillers such as clays, kaolin, or reinforced nanoparticles or nanoparticles made of thermosetting material, and powder fillers such as talc. The degree of incorporation of reinforcing and/or bulking filler is in accordance with the standards in the composite material field. It may, for example, be a degree of filler of from 1% to 50% by weight, relative to the total weight of the composition.
- The composition may comprise, in addition to the modified polyamide of the invention, one or more other polymers, preferably polyamides or copolyamides.
- The composition according to the invention may also comprise additives normally used for the production of polyamide compositions. Thus, mention may be made of lubricants, flame retardants, plasticizers, nucleating agents, catalysts, agents for improving impact strength, such as optionally grafted elastomers, light and/or heat stabilizers, antioxidants, antistatics, colorants, mattifying agents, molding aids or other conventional additives.
- These fillers and additives can be added to the modified polyamide by standard means suited to each filler or additive, such as, for example, during melt blending or polymerization.
- The thermoplastic compositions are generally obtained by mixing the various compounds that go to make up the composition, the thermoplastic compounds being in molten form. The process is carried out at more or less high temperature, and at more or less high shear force depending on the nature of the various compounds. The compounds can be introduced simultaneously or successively. An extrusion device in which the material is heated, subjected to a shear force and conveyed along, is generally used. Such devices are entirely known to those skilled in the art.
- According to a first embodiment, all the compounds are melt blended during a single operation, for example during an extrusion operation. It is, for example, possible to blend granules of the polymeric materials, and to introduce them into the extrusion device in order to melt them and to subject them to a more or less large shear stress.
- According to particular embodiments, it is possible to prepare pre-blends, which may or may not be melt pre-blends, of some of the compounds before preparation of the final composition.
- The composition according to the invention, when it is prepared using an extrusion device, is preferably conditioned in the form of granules. The granules are intended to be formed by means of processes involving melting so as to obtain articles. The articles are thus made up of the composition. According to one customary embodiment, the modified polyamide is extruded in the form of rods, for example in a twin-extrusion device, and said rods are then cut into granules. The molded components are then prepared by melting the granules produced above and feeding the molten composition into injection molding devices.
- The use of the compositions according to the invention is particularly advantageous in the context of the electrical industry, in particular for the molding of components of large sizes or with a complex geometry.
- Specific terms are used in the description in such a way as to facilitate understanding of the principle of the invention. It should nevertheless be understood that no limitation of the scope of the invention is envisioned with the use of these specific terms. The term “and/or” includes the meanings and, or, and also all the other possible combinations of elements connected to this term.
- Other details or advantages of the invention will emerge more clearly in view of the examples below, given only by way of indication.
- The following compounds are used:
-
- PA1: Polyamide 66 having an MFI of 2.7 g/10 minutes (according to the ISO1133 standard measured at 275° C. with a load of 325 g) and an IV of 140. Contents of following end groups: amine end groups=40 meq/kg, carboxylic end groups=60 meq/kg.
- PA2: Polyamide 66 having an MFI of 30 g/10 minutes (according to the ISO1133 standard measured at 275° C. with a load of 325 g) and an IV of 98. Contents of following end groups: amine end groups=28 meq/kg, carboxylic end groups=90 meq/kg. Obtained by adding 0.7 mol % of benzoic acid at the beginning of polymerization.
- Glass fibers: Vetrotex 99B.
- E1: ethylene/acrylicester/glycidyl methacrylate terpolymer elastomer (8% by weight of glycidyl methacrylate), sold under the name Lotader® AX8900 by the company Arkema.
- E2: ethylene/butyl ester acrylate copolymer elastomer, sold under the name Lotryl® 30 BA 02 by the company Atofina.
- E3: ethylene/n-butyl acrylate/glycidyl methacrylate copolymer elastomer, sold under the name Elvaloyl® PTW by the company DuPont.
- E4: ethylene/maleic anhydride copolymer elastomer, sold under the name Exxelor® VA 1840 by the company Exxon Mobil.
- E5: ethylene/maleic anhydride copolymer elastomer, sold under the name Fusabond® N MN493D by the company DuPont.
- E6: ethylene/acrylic acid copolymer elastomer, sold under the name Primacor® EAA 449 by the company Dow.
- E7: ethylene/vinyl acetate copolymer elastomer, sold under the name Escorene® UL 02528 by the company Exxon Mobil.
- Additives: EBS wax, and nigrosine sold under the name 54/1033 by the company Ferroplast.
- The compositions are prepared by melt blending, using a Werner and Pfleiderer ZSK twin-screw extruder, the polyamides, 5% by weight of elastomers, 30% by weight of glass fibers, and 1.3% by weight of additives. The extrusion conditions are the following: temperature: between 240 and 280° C., rotation speed: between 200 and 300 rpm, flow rate between 25 and 60 kg/hour.
- The various compositions prepared are shown in Table 1:
-
TABLE 1 Unnotched Spiral Charpy test impact Examples Polymer Elastomer (cm) (KJ/m2) C1 PA1 — 25 86.3 C2 PA1 E1 24 89.7 C3 PA2 — 46 58.2 1 PA2 E1 47 82.2 2 PA2 E3 45 84.4 3 PA2 E4 45 88.1 4 PA2 E5 44 88.8 5 PA2 30% E1 + 45 86.8 70% E2 6 PA2 15% E1 + 46 80.8 85% E2 7 PA2 E6 41 78.8 8 PA2 E7 46 79.7 The unnotched Charpy impact strength is measured according to ISO standard 179/1eU. - The spiral test makes it possible to quantify the fluidity of the compositions by melting the granules and injecting them into a spiral-shaped mold with a semicircular cross section of thickness 2 mm and of width 4 cm, in a BM-Biraghi 85T press at a barrel temperature of 275° C. and a mold temperature of 80° C. and with a maximum injection pressure of 130 bar, which corresponds to an injection time of approximately 0.4 seconds (the result is expressed as length of mold correctly filled by the composition).
- It is thus observed that the compositions obtained exhibit excellent compatibilization between the polyamide of the invention and the grafted elastomers, thereby resulting in the obtaining of articles having an excellent balance between mechanical properties and melt flow. It is, moreover, observed that the articles of Examples 1-8 exhibit a good surface appearance.
Claims (18)
1.-13. (canceled)
14. A polymer composition comprising at least:
a) a polyamide 6 or 66 obtained via a process of polymerization of the polyamide 6 or 66 monomers in the presence of monofunctional and/or difunctional compounds comprising carboxylic acid or amine functional groups, said polyamide having a melt flow index of greater than or equal to 10 g/10 min. according to the ISO1133 standard measured at a temperature of 275° C. with a load of 325 g; and
b) an impact modifier comprising functional groups that react with the polyamide a).
15. The polymer composition as defined by claim 14 , wherein the molecular weight Mn of the polyamide ranges from 3,000 to 25,000 g/mol.
16. The polymer composition as defined by claim 14 , wherein the polydispersity index of the polyamide is less than or equal to 2.
17. The polymer composition as defined by claim 14 , wherein the polyamide is obtained by adding, at the beginning, during or at the end of polymerization, aliphatic or aromatic, monocarboxylic or dicarboxylic acids and/or aliphatic or aromatic, monoamines or diamines.
18. The polymer composition as defined by claim 14 , wherein the polyamide has a melt flow index ranging from 10 to 50 g/10 min.
19. The polymer composition as defined by claim 14 , wherein the polyamide has a melt flow index ranging from 20 to 40 g/10 min.
20. The polymer composition as defined by claim 14 , wherein the impact modifiers are oligomeric or polymeric compounds comprising at least one of the following monomers, or a mixture thereof: ethylene, propylene, butene, isoprene, diene, acrylate, butadiene, styrene, octene, acrylonitrile, acrylic acid, methacrylic acid, vinyl acetate, vinyl esters such as acrylic and methacrylic esters, and glycidyl methacrylate.
21. The polymer composition as defined by claim 14 , wherein the impact modifiers comprise an elastomeric base selected from the group consisting of polyethylenes, polypropylenes, polybutenes, polyisoprenes, ethylene-propylene rubbers (EPRs), ethylene-propylene-diene rubbers (EPDMs), ethylene butene rubbers, ethylene acrylate rubbers, butadiene styrene rubbers, butadiene acrylate rubbers, ethylene octene rubbers, butadiene acrylonitrile rubbers, ethylene acrylic acids (EAAs), ethylene vinyl acetate (EVAs), ethylene acrylic esters (EEAs), acrylonitrile-butadiene-styrene (ABS) copolymers, styrene-ethylene-butadiene-styrene (SEBS) block copolymers, styrene-butadiene-styrene (SBS) copolymers, core-shell elastomers of methacrylate-butadiene-styrene (MBS) type, or blends of at least two of the elastomers listed above.
22. The polymer composition as defined by claim 14 , wherein the functional groups of the impact modifier, that are capable of reacting chemically with the polyamide a) are selected from the group consisting of acids, carboxylic acids, salified acids, esters, acrylates and methacrylates, ionomers, glycidyl groups, epoxy groups, glycidyl esters, anhydrides, maleic anhydrides, maleimides, and mixtures thereof.
23. The polymer composition as defined by claim 14 , wherein the impact modifiers are selected from the group consisting of ethylene/acrylic ester/glycidyl methacrylate terpolymers, ethylene/butyl ester acrylate copolymers, ethylene/n-butyl acrylate/glycidyl methacrylate copolymers, ethylene/maleic anhydride copolymers, maleic anhydride-grafted styrene/maleimide copolymers, copolymers of styrene/ethylene/butylene/styrene modified with maleic anhydride, maleic anhydride-grafted styrene/acrylonitrile copolymers, maleic anhydride-grafted acrylonitrile/butadiene/styrene copolymers, and hydrogenated congeners thereof.
24. The polymer composition as defined by claim 14 , wherein the proportion of impact modifiers present therein ranges from 0.1% to 10% by weight.
25. The polymer composition as defined by claim 14 , comprising at least one reinforcing and/or bulking filler.
26. A method for producing a polymer composition as defined by claim 14 , comprising melt blending said polyamide a) and said impact strength modifiers b).
27. The polymer composition as defined by claim 14 , comprising at least one polyamide 6.
28. The polymer composition as defined by claim 14 , comprising at least one polyamide 66.
29. A shaped article product of reaction between the polyamide and the impact modifier as defined by claim 14 .
30. A shaped article product of reaction between the constituents of the polymer composition as defined by claim 14 .
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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FR0701302 | 2007-02-23 | ||
FR0701302A FR2913023B1 (en) | 2007-02-23 | 2007-02-23 | THERMOPLASTIC POLYMER COMPOSITION BASED ON POLYAMIDE |
PCT/EP2008/052134 WO2008107314A1 (en) | 2007-02-23 | 2008-02-21 | Polyamide based thermoplastic polymer composition |
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PCT/EP2008/052134 A-371-Of-International WO2008107314A1 (en) | 2007-02-23 | 2008-02-21 | Polyamide based thermoplastic polymer composition |
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US14/471,888 Continuation US9156982B2 (en) | 2007-02-23 | 2014-08-28 | Polyamide-based thermoplastic polymer compositions |
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US20100130677A1 true US20100130677A1 (en) | 2010-05-27 |
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US12/527,014 Abandoned US20100130677A1 (en) | 2007-02-23 | 2008-02-21 | Polyamide-based thermoplastic polymer compositions |
US14/471,888 Active US9156982B2 (en) | 2007-02-23 | 2014-08-28 | Polyamide-based thermoplastic polymer compositions |
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EP (1) | EP2121844B1 (en) |
JP (3) | JP2010519373A (en) |
CN (1) | CN101688059B (en) |
BR (1) | BRPI0807294B1 (en) |
CA (1) | CA2678474A1 (en) |
FR (1) | FR2913023B1 (en) |
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Also Published As
Publication number | Publication date |
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BRPI0807294B1 (en) | 2019-04-09 |
FR2913023A1 (en) | 2008-08-29 |
BRPI0807294A2 (en) | 2014-05-06 |
JP2013241628A (en) | 2013-12-05 |
EP2121844B1 (en) | 2016-08-10 |
JP2010519373A (en) | 2010-06-03 |
CN101688059B (en) | 2013-06-19 |
US20150045494A1 (en) | 2015-02-12 |
FR2913023B1 (en) | 2009-04-10 |
EP2121844A1 (en) | 2009-11-25 |
US9156982B2 (en) | 2015-10-13 |
JP2016047936A (en) | 2016-04-07 |
CA2678474A1 (en) | 2008-09-12 |
CN101688059A (en) | 2010-03-31 |
WO2008107314A1 (en) | 2008-09-12 |
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