CN116997611A - Polyamide compositions with functionalized polyolefins and mobile electronic device components containing them - Google Patents
Polyamide compositions with functionalized polyolefins and mobile electronic device components containing them Download PDFInfo
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- CN116997611A CN116997611A CN202280022371.2A CN202280022371A CN116997611A CN 116997611 A CN116997611 A CN 116997611A CN 202280022371 A CN202280022371 A CN 202280022371A CN 116997611 A CN116997611 A CN 116997611A
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- polyamide
- functionalized polyolefin
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- 239000000203 mixture Substances 0.000 title claims abstract description 164
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 133
- 229920002647 polyamide Polymers 0.000 title claims description 86
- 239000004952 Polyamide Substances 0.000 title claims description 82
- 229920000642 polymer Polymers 0.000 claims abstract description 126
- 239000003365 glass fiber Substances 0.000 claims abstract description 89
- 239000004954 Polyphthalamide Substances 0.000 claims abstract description 56
- 229920006375 polyphtalamide Polymers 0.000 claims abstract description 56
- 150000001408 amides Chemical class 0.000 claims description 48
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- -1 polyethylene Polymers 0.000 claims description 29
- 239000004743 Polypropylene Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 229920001155 polypropylene Polymers 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 19
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 17
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920002367 Polyisobutene Polymers 0.000 claims description 3
- 150000002118 epoxides Chemical class 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229920001748 polybutylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920000306 polymethylpentene Polymers 0.000 claims description 3
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- 239000002253 acid Substances 0.000 abstract description 25
- 125000005521 carbonamide group Chemical group 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 38
- 239000011521 glass Substances 0.000 description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 239000000654 additive Substances 0.000 description 15
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- 230000007547 defect Effects 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
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- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 6
- 239000012783 reinforcing fiber Substances 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
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- 230000002829 reductive effect Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012760 heat stabilizer Substances 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
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- 239000000314 lubricant Substances 0.000 description 4
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 4
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- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- 238000002156 mixing Methods 0.000 description 3
- 229920005606 polypropylene copolymer Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- MLXUAMJSJWGSEX-UHFFFAOYSA-N 10-(7-azabicyclo[3.3.1]nona-1(9),2,4-trien-7-yl)-10-oxodecanamide Chemical compound C1=CC(CN(C(=O)CCCCCCCCC(=O)N)C2)=CC2=C1 MLXUAMJSJWGSEX-UHFFFAOYSA-N 0.000 description 2
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- GAGWMWLBYJPFDD-UHFFFAOYSA-N 2-methyloctane-1,8-diamine Chemical compound NCC(C)CCCCCCN GAGWMWLBYJPFDD-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 239000004609 Impact Modifier Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 229920006883 PAMXD6 Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229920006020 amorphous polyamide Polymers 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 2
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 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 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
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- 150000002739 metals Chemical class 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
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- 239000012764 mineral filler Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229920006114 semi-crystalline semi-aromatic polyamide Polymers 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
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- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 239000004760 aramid Substances 0.000 description 1
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- 150000004984 aromatic diamines Chemical class 0.000 description 1
- QFNNDGVVMCZKEY-UHFFFAOYSA-N azacyclododecan-2-one Chemical compound O=C1CCCCCCCCCCN1 QFNNDGVVMCZKEY-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
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- GKHRLTCUMXVTAV-UHFFFAOYSA-N dimoracin Chemical compound C1=C(O)C=C2OC(C3=CC(O)=C(C(=C3)O)C3C4C(C5=C(O)C=C(C=C5O3)C=3OC5=CC(O)=CC=C5C=3)C=C(CC4(C)C)C)=CC2=C1 GKHRLTCUMXVTAV-UHFFFAOYSA-N 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
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- 229910001416 lithium ion Inorganic materials 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- ORECYURYFJYPKY-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine;2,4,6-trichloro-1,3,5-triazine;2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N.ClC1=NC(Cl)=NC(Cl)=N1.C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 ORECYURYFJYPKY-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Described herein are polymer compositions comprising polyphthalamide having a carbon/amide molar ratio of greater than 8, a functionalized polyolefin, and glass fibers, wherein the weight ratio of the functionalized polyolefin to the total weight of the polyphthalamide and the functionalized polyolefin in the polymer composition is greater than 0% and up to 27%. Surprisingly, it was found that these polymer compositions have excellent dielectric properties, acid resistance and improved mechanical properties, in particular tensile elongation and unnotched izod impact, relative to the corresponding polymer compositions omitting such functionalized polyolefin. The polymer composition can be desirably incorporated into mobile electronic device components due to excellent properties.
Description
Cross Reference to Related Applications
The present application claims priority from U.S. provisional application No. 63/152392, filed 2/23 in 2021, and european patent application No. 21182545.0, filed 6/29 in 2021, the disclosures of which are incorporated herein by reference in their entireties for all purposes.
Technical Field
The present invention relates to a polymer composition comprising polyphthalamide, functionalized polyolefin and glass fiber, which polymer composition has excellent dielectric properties, improved acid resistance and improved mechanical properties. The invention also relates to articles, such as mobile electronic device parts, comprising the polymer composition.
Background
The popularity of metal/plastic hybrid designs is growing rapidly in the consumer electronics industry. Designers prefer to use metal as the main housing and chassis material for portable electronic devices such as cell phones, notebook computers, tablet computers, personal Digital Assistants (PDAs), etc., due to the functional benefits that metal provides in terms of aesthetic and useful characteristics such as such body strength and electromagnetic shielding. However, metals have shortcomings in critical areas such as radio transparency, colorability, and cost. In addition, the body of some mobile devices may include portions with complex geometric configurations that may be difficult, expensive, or otherwise inefficient to manufacture from metal. Thus, the portion of the mobile device body having the complex geometric configuration may also be formed of plastic. Because of these problems, hybrid design solutions, i.e. capable of combining the benefits of metal and plastic according to exact functional requirements, are generally preferred.
Various techniques may be used for plastic metal hybrid designs. In recent decades, nano-molding technology has been widely adopted in the consumer electronics industry to replace traditional metal insert molding. The cost of the system for manufacturing metal parts is reduced compared to conventional metal insert molding routes. The polymeric structure may be directly overmolded, injection molded, and/or transfer molded onto the metal substrate. For example, a polymeric part may be insert molded or over molded onto a metal part to form a component of a mobile device.
The glass fiber reinforced polymer resin enables high adhesion between metal and plastic. The polymer resin reinforced with glass fibers also enables shrinkage reduction and enhanced mechanical properties.
Because metals are typically colored, a process step known as anodization is often used after molding the plastic metal hybrid part. In anodic oxidation, the material undergoes multiple steps of exposure to corrosive acids and solutions to achieve the protective coating and desired color. Thus, chemical resistance, and in particular acid resistance, is a requirement for the choice of polymer resins, thereby limiting the use of certain polymers such as polyamides. Polyamide compositions and in particular polyamide compositions comprising glass fibers are widely used in mobile electronic device parts due to their reduced weight and high mechanical properties. Polyamides are a class of materials that are highly valued for their resistance to alkaline hydrolysis, however their sensitivity to acid-catalyzed hydrolysis limits their use in applications requiring anodic oxidation.
Thus, when the polymer resin in the plastic part is acid sensitive, it may be desirable to mask the surface of the polymer part prior to anodic oxidation to prevent acid attack, or it may be desirable to first anodize the metal substrate and then directly overmold, injection mold, and/or transfer mold the polymer resin onto the anodized metal substrate.
It is generally better when the complete surfaces of one or more plastic parts and one or more metal parts of an electronic device component are anodized such that no masking during the anodization or prior anodization of the metal parts is required, thereby improving the efficiency of the manufacturing process. In this way, the anodized coating provides a seamless appearance even though the component is formed from both plastic and metal parts, thereby improving the aesthetic appearance of the component of the portable electronic device. In this regard, the coating formed by anodic oxidation may also be dyed to have various colors and/or may be subjected to various surface finishes to further promote the aesthetic appearance of the portable electronic device.
The present invention aims to provide polyamide compositions having improved mechanical properties and also acid resistance. These polyamide compositions will be particularly suitable for use in the manufacture of articles, such as mobile device parts, that can be subjected to acid exposure, such as during anodic oxidation.
Disclosure of Invention
A first aspect of the invention relates to a polymer composition comprising:
functionalized Polyolefin (PO) f )，
Polyamide (PA) selected from polyphthalamides (PPA) having a carbon to amide molar ratio of greater than 8,
glass fiber, and
functionalized Polyolefin (PO) f ) The weight ratio is greater than 0% and at most 27%,
wherein the method comprises the steps of
-the PO f The weight ratio is given by:and is also provided with
-W PA And W is PO The weight of the polyamide and the functionalized polyolefin in the polymer composition, respectively;
wherein the method comprises the steps of
The functionalized polyolefin comprises recurring units R respectively represented by the formula PO1 And R is PO2 ：
Wherein R is 5 To R 8 Independently selected from the group consisting of: hydrogen and a catalyst comprising- (CH) 2 ) m -CH 3 Alkyl represented, wherein m is an integer from 0 to 5; r is R 9 To R 12 Independently selected from the group consisting of: hydrogen, from- (CH) 2 ) m’ -CH 3 Alkyl groups represented, wherein m is an integer from 0 to 5, and reactive groups reactive with amine or carboxylic acid groups of the polyamide; and wherein R is 9 To R 12 At least one of which is a reactive group, and
the functionalized polyolefin comprises from 0.05 to 1.5mol% of recurring units R PO2 。
A second aspect of the invention relates to a mobile electronic device component comprising a polymer composition as described herein, preferably the mobile electronic device component is an antenna such as a mobile electronic antenna, an antenna window, an antenna housing or a mobile electronic housing.
A third aspect of the invention relates to a method for manufacturing a mobile electronic device component, the method comprising: the polymer composition as described herein is first overmolded, injection molded, or transfer molded onto a metal substrate to form a component, and then the component is subjected to anodic oxidation.
Various aspects, advantages, and features of the present invention will be more readily understood and appreciated by reference to the following detailed description and examples.
Drawings
FIG. 1 shows when PO f In the case of maleic anhydride-functionalized polypropylene copolymers (MA-PP), polyamide/PO f The blend was 0% to 14.4% different PO f Unnotched Izod impact in weight ratio (measured according to ASTM D256).
FIG. 2 shows when PO f In the case of maleic anhydride-functionalized polypropylene copolymers (MA-PP), polyamide/PO f The blends were relative to 0% to 14.4% of the various POs f Dielectric constant D at 2.45GHz k (measured according to ASTM D2520).
Definition of the definition
In this descriptive specification, some terms are intended to have the following meanings.
In this specification, selecting an element from a set of elements also explicitly describes:
selecting two or several elements from the group,
-selecting an element from a subset of elements consisting of the set of elements from which one or more elements have been removed.
In the following paragraphs of this specification, even any description described with respect to specific embodiments may be applicable to and interchangeable with other embodiments of the present disclosure. Each embodiment so defined may be combined with another embodiment unless otherwise indicated or clearly incompatible. Furthermore, it is to be understood that elements and/or features of a composition, product or article, method or use described in this specification may be combined in all possible ways with other elements and/or features of the composition, product or article, method or use, either explicitly or implicitly, without departing from the scope of this specification.
In this specification, the description of a series of values for a variable defined by a lower limit, or an upper limit, or both, also includes embodiments in which the variable is correspondingly selected within the numerical range: the lower limit is not included, or the upper limit is not included, or both the lower limit and the upper limit are not included. Any recitation of numerical ranges by endpoints herein includes all numbers subsumed within that recited range, as well as the endpoints and equivalents of that range.
The term "comprising" encompasses "consisting essentially of … … and also" consisting of … ….
As used herein, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise.
Furthermore, if the terms "about," "about," or "about (ca.)" are used prior to a numerical value, then the present teachings also include the particular numerical value itself, unless explicitly indicated otherwise. As used herein, the terms "about," "about," or "approximately" refer to a variation from nominal of + -10%, unless explicitly indicated otherwise.
The disclosures of all patent applications and publications cited herein are hereby incorporated by reference to the extent that they provide exemplary, procedural or other details supplementary to those set forth herein. The description of the present application should take precedence if the disclosure of any patent, patent application, or publication incorporated by reference herein conflicts with the description of the present application to the extent that the term "unclear".
Detailed Description
Surprisingly, it has been found that in order to improve the tensile elongation and the unnotched izod impact value of a polyphthalamide-containing composition, the weight ratio ("PO") of functionalized polyolefin can be greater than 0% and up to 27%, preferably up to 25%, or up to 20%, or up to 15% f Weight ratio ") of functionalized polyolefin, wherein the PO is f The weight ratio is given by:and is also provided with
W PA And W is PO The weight of polyamide and functionalized polyolefin in the polymer composition, respectively. PO in Polymer compositions f The weight ratio is preferably 1% to 27%, preferably 2% to 25%, more preferably 3% to 20%, or 3% to 15%, or 3.5% to 14.5%, or 3.6% to 14.5%.
At PO f In the weight ratio, the weight of polyamide in the polymer composition according to the invention is preferably chosen from those having a carbon to amide molar ratio (C/CONH) or "C/acyl" of greater than 8, present in the polymer compositionAmine molar ratio "weight of one or more polyamides of the polyphthalamide.
It has further unexpectedly been found that in order to improve the acid resistance of a polyphthalamide containing composition, polyphthalamides having a C/amide molar ratio of greater than 8, or at least 8.1, or at least 8.2, or at least 8.3, or at least 8.4, or at least 8.5, or at least 9, can be selected.
Polyamide component (PA)
The polymer composition according to the invention comprises a polyamide selected from polyphthalamides (PPA) having a C/amide molar ratio of greater than 8.
The polyphthalamide in the polymer composition preferably has a C/amide molar ratio of at least 8.1, or at least 8.2, or at least 8.3, or at least 8.4, or at least 8.5, or at least 9. The C/amide molar ratio of polyphthalamide may be at most 15, or at most 13, or at most 12. Suitable C/amide molar ratios for polyphthalamides may range from greater than 8 up to 15, or 8.1 to 14, or 8.5 to 13, or 9 to 12.
As used herein, polyphthalamides (PPA) are generally obtained by polycondensation between at least one diacid and at least one diamine, wherein at least 55 mole percent of the diacid moieties of the repeat units in the PPA polymer chain are terephthalic acid and/or isophthalic acid, and wherein at least one diamine is aliphatic. Suitable aliphatic diamines are diamines having at least 6 carbon atoms and up to 14 carbon atoms, such as hexamethylenediamine, nonamethylenediamine, 2-methyl-octamethylenediamine and decamethylenediamine; preferred aliphatic diamines have more than 6 carbon atoms and up to 14 carbon atoms; more preferred aliphatic diamines have more than 7 carbon atoms and up to 12 carbon atoms. If an aliphatic diacid is used during polycondensation to form PPA, suitable aliphatic diacids are adipic acid, sebacic acid, and dodecanedioic acid; however, preferred aliphatic diacids have more than 6 carbon atoms and up to 12 carbon atoms, such as sebacic acid and dodecanedioic acid. Polyphthalamide (PPA) is considered a subset of semi-aromatic polyamides.
In some embodiments, the polyamide in the polymer composition is at least one polyphthalamide having a C/amide molar ratio of >8 selected from the group consisting of: PA10, T/10, I; PA10, T; PA9, T; and any combination thereof.
In some embodiments, the concentration of the at least one polyphthalamide in the polymer composition having a C/amide molar ratio of >8 is
-at least 40wt.%, or at least 45wt.%, or at least 50wt.%, or at least 54wt.% of such polyphthalamide having a C/amide molar ratio of >8, based on the total weight of the polymer composition, and/or
Up to 80wt.%, or up to 78wt.%, or up to 77wt.%, or up to 75wt.% of such polyphthalamide having a C/amide molar ratio of >8, based on the total weight of the polymer composition.
In some embodiments, the concentration of the at least one polyphthalamide in the polymer composition having a C/amide molar ratio of >8 is 30wt.% to 78wt.%, or 40wt.% to 77wt.%, or 45wt.% to 77wt.%, or 50wt.% to 70wt.%, or 50wt.% to 80wt.%, or 55wt.% to 78wt.% of such polyphthalamide, based on the total weight of the polymer composition.
In some embodiments, the polymer composition comprises a plurality of different polyphthalamides according to the description above having a C/amide molar ratio of > 8. In some such embodiments, the total concentration of different polyphthalamides having a C/amide molar ratio of >8 is within the ranges described above.
In a preferred embodiment, the polymer composition does not comprise a semiaromatic polyamide or polyphthalamide obtained by polycondensation between a diacid and a diamine monomer, one of which is aliphatic and has 6 or less carbon atoms.
In a preferred embodiment, the polymer composition does not comprise an aliphatic polyamide.
In a preferred embodiment, the polymer composition does not comprise a polyamide having a number average molecular weight of less than 1600.
In some embodiments, the polymer composition does not comprise a semiaromatic polyamide that is not a polyphthalamide, and/or does not comprise a polyphthalamide having a C/amide molar ratio of up to 8.
In some embodiments, the polymer composition does not comprise a polyamide resulting from polycondensation wherein the diacid does not comprise terephthalic acid and/or isophthalic acid.
Optionally one or more polyamide components
In an alternative embodiment, the polymer composition optionally comprises another polyamide than polyphthalamide having a C/amide molar ratio of > 8.
The polymer composition may further comprise at least one semi-aromatic polyamide that is not a polyphthalamide, at least one polyphthalamide having a C/amide molar ratio of up to 8, at least one aliphatic polyamide, or a combination thereof.
Aliphatic or semiaromatic polyamides (excluding polyphthalamides) are generally obtained by polycondensation between at least one aromatic or aliphatic saturated diacid and at least one aliphatic saturated or aromatic primary diamine, lactam, amino acid or mixtures of these different monomers. Suitable aliphatic diamines are hexamethylenediamine, nonamethylenediamine, 2-methyl-octamethylenediamine and decamethylenediamine. Suitable aromatic diamines are meta-xylylenediamine (MXDA) and para-xylylenediamine (PXDA). Suitable aliphatic diacids are adipic acid, sebacic acid, and dodecanedioic acid. Suitable lactams are caprolactam, undecanolactam and laurolactam. Suitable amino acids are 11-aminoundecanoic acid and 12-aminolauric acid. Aromatic diacids such as terephthalic acid and isophthalic acid are not used in the polycondensation of such polyamides, or less than 55 mole%, preferably up to 50 mole%, more preferably up to 45 mole% of the diacid moieties in the semiaromatic polyamide chains are terephthalic acid and/or isophthalic acid.
As used herein, an aliphatic polyamide comprises at least 50 mole% of recurring units having amide linkages (-NH-CO-) and which do not contain any aromatic groups. In other words, the diacids and diamines, lactams or amino acids forming the recurring units of the polyamide by polycondensation do not contain any aromatic groups.
In some embodiments, the polymer composition may further comprise a semi-aromatic polyamide that is not a polyphthalamide, such as PAMXD6 (poly (m-xylylene adipamide)), PAMXD10 (poly (m-xylylene sebacamide)), and/or PAPXD10 (poly (m-xylylene sebacamide)), and preferably may further comprise PAPXD10.
Examples of polyphthalamides having a C/amide molar ratio of up to 8 are PA6, T/6, I or PA6, T/6,6 or PA6, I/6,6 or PA6,6/6, I or PA6,6/6, T.
In some embodiments, the polymer composition may comprise a polyphthalamide selected from the group consisting of: PA10, T/10, i, PA10, T, PA, T and any combination thereof, and at least one semiaromatic polyamide selected from the group consisting of: PA6, T/6, i, PAMXD6, PAPXD10, and any combination thereof.
In some embodiments, the polymer composition may further comprise an aliphatic polyamide.
Suitable aliphatic polyamides may be selected from the group consisting of: PA6,10, PA10, PA11, PA12 and PA10,12; or preferably selected from the group consisting of: PA10, PA11, PA12 and PA10,12.
In some embodiments, the concentration of all polyamides in the polymer composition is at least 40wt.%, or at least 45wt.%, or at least 50wt.%, or at least 54wt.%, and/or at most 80wt.%, or at most 78wt.%, or at most 77wt.%, or at most 75wt.% based on the total weight of the polymer composition. In some embodiments, the concentration of all polyamides in the polymer composition is 30wt.% to 78wt.%, or 40wt.% to 77wt.%, or 45wt.% to 77wt.%, or 50wt.% to 70wt.%, or 50wt.% to 80wt.%, or 55wt.% to 78wt.%, based on the total weight of the polymer composition.
In some embodiments, when the polymer composition comprises at least one polyphthalamide having a C/amide molar ratio of >8 and one or more other polyamides, the weight ratio of such one or more polyphthalamides is greater than the weight ratio of such one or more other polyamides, such weight ratio being based on the total weight of all polyamides in the polymer composition.
The polyamide in the polymer composition may be a semi-crystalline polyamide or an amorphous polyamide.
As used herein, semi-crystalline polyamides include a heat of fusion ("Δh") of at least 5 joules/gram (J/g) measured using differential scanning calorimetry at a heating rate of 20 ℃/min f "). Similarly, as used herein, an amorphous polyamide includes a Δh of less than 5J/g measured using differential scanning calorimetry at a heating rate of 20 ℃/min f 。ΔH f Can be measured according to ASTM D3418. In some embodiments, ΔH f Is at least 20J/g, at least 30J/g or at least 40J/g.
In some embodiments, the polyamide has a Tg of at least 100 ℃, at least 110 ℃, or at least 115 ℃. Additionally or alternatively, in some embodiments, the Polyamide (PA) has a Tg of no more than 200 ℃, no more than 180 ℃, no more than 160 ℃, no more than 150 ℃, no more than 140 ℃, or no more than 135 ℃. In some embodiments, the Polyamide (PA) has a Tg of 100 ℃ to 150 ℃, 110 ℃ to 140 ℃, or 115 ℃ to 135 ℃. In some embodiments, the polyamide has a Tg of 100 ℃ to 200 ℃, 110 ℃ to 180 ℃, or 115 ℃ to 160 ℃. In some embodiments, the polyamide has a melting temperature ("Tm") of at least 260 ℃, at least 265 ℃, at least 290 ℃, at least 300 ℃, or at least 310 ℃. Additionally or alternatively, in some embodiments, the polyamide has a Tm of no more than 360 ℃, no more than 350 ℃, or no more than 340 ℃. In some embodiments, the polyamide has a Tm of 290 ℃ to 360 ℃, 300 ℃ to 350 ℃, or 310 ℃ to 340 ℃. Tg and Tm can be measured according to ASTM D3418.
Functionalized polyolefin component (PO) f )
The polymer composition comprises a functionalized polyolefin. Polyolefin, as used herein, means any polymer having at least 50 mole% of repeating units R PO Is a polymer of (a). In some embodiments, the repeating unit R PO Is at least 60 mole%, at least 70 mole%, at least 80 mole%, at least 90 mole%, at least 95 mole%, at least 99 mole%, or at least 99.9 mole%. As used herein, unless explicitly stated otherwise, mol% is relative to the total number of repeating units in the polyolefin. Repeat unit R PO Represented by:
wherein R is 1 To R 4 Independently selected from the group consisting of: hydrogen and a catalyst comprising- (CH) 2 ) n -CH 3 Alkyl groups represented, wherein n is an integer from 0 to 5. For clarity, when n is zero, the alkyl group is methyl.
The functionalized polyolefin is a polyolefin comprising reactive groups that react with amine or carboxylic acid groups on the polyamide, thereby creating covalent bonds (e.g., amide bonds) between the polyolefin and one or more polyamides in the polymer composition. In other words, the functionalized polyolefin comprises at least some of the units according to formula (1) and R PO Different repeating units R PO Wherein R is 1 To R 4 Is replaced by a reactive group. Of course, in embodiments in which the polyolefin is fully functionalized, the functionalized polyolefin includes repeat units R × PO And is free of repeating units R PO 。
Desirable polyolefins include, but are not limited to, polyethylene, polypropylene, polymethylpentene, polybutene-1, polyisobutylene, ethylene propylene rubber, and ethylene propylene diene monomer rubber; preferably the polyolefin is polypropylene. Desirable reactive groups include, but are not limited to, maleic anhydride, epoxide, isocyanate, and acrylic acid. Of course, in the polymer composition, the polyolefin is covalently bonded to the polyamide through residues formed by the reaction of at least some of the reactive groups on the polyolefin with amine or carboxylic acid groups on the polyamide. For ease of reference, it is understood that reference to reactive groups on the functionalized polyolefin polymer in the polymer composition refers to any unreacted reactive groups on the functionalized polyolefin as well as residues formed by the reaction between the reactive groups and the amine or carboxylic acid on the polyamide. For example, one of ordinary skill in the art will appreciate that reference to a maleic anhydride functionalized polyolefin in a polymer composition refers to any unreacted maleic anhydride groups on the polyolefin polymer as well as residues formed by the reaction of maleic anhydride with amine groups on the polyamide.
In some embodiments, the reactive group is represented by a formula selected from the group of formulas:
wherein R is 17 And R is 20 Selected from hydrogen and alkyl, and R 18 、R 19 、R 21 And R is 22 Selected from the group consisting of bonds and alkyl groups. Preferably, R 17 And R is 20 Are all hydrogen. Preferably, R 18 、R 19 、R 21 And R is 22 Are keys. For clarity, the "×" in formulae (2) to (5) indicates and repeats R × PO Is a bond to carbon of (c).
In a preferred embodiment, the functionalized polyolefin may be functionalized with a reactive group selected from the group consisting of maleic anhydride, epoxide, isocyanate and acrylic acid, preferably the reactive group is maleic anhydride.
The polyolefin may be functionalized at its chain ends or along the main chain (or both). In some embodiments in which the polyolefin is functionalized along the backbone, the functionalized polyolefin comprises a total of at least 50 mole percent of repeat units R PO1 Repeat unit R PO2 (defined below). In some embodiments, the repeat unit R in the functionalized polyolefin PO1 And R is PO2 Is at least 60 mole%, at least 70 mole%, at least 80 mole%, at least 90m based on the total concentration of repeat units in the functionalized polyolefinMol%, at least 95mol%, or at least 99mol%. R as described above PO1 And R is PO2 Within the range of the sum concentration of (1), in some embodiments, the repeating unit R PO2 The concentration of (c) is at least 0.05mol% to 10mol%, 0.05mol% to 8mol%, 0.05mol% to 6mol%, 0.05mol% to 4mol%, 0.05mol% to 2mol%, 0.05mol% to 1.5mol%, or 0.1mol% to 1.5mol% of the total concentration of repeating units in the functionalized polyolefin.
Repeat unit R PO1 And R is PO2 Represented by the following formulas (6) and (7), respectively:
wherein R is 5 To R 8 Independently selected from the group consisting of: hydrogen and a catalyst comprising- (CH) 2 ) m -CH 3 Alkyl represented, wherein m is an integer from 0 to 5; r is R 9 To R 12 Independently selected from the group consisting of: hydrogen, from- (CH) 2 ) m’ -CH 3 Alkyl groups represented, wherein m is an integer from 0 to 5, and reactive groups reactive with amine or carboxylic acid groups of the polyamide; and wherein R is 9 To R 12 At least one of which is a reactive group. In some embodiments, the reactive group is represented by a formula selected from the group consisting of formulas (2) through (5). In some embodiments, R 5 To R 7 Are all hydrogen and R 8 is-CH 3 . Additionally or alternatively, in some embodiments, R 9 And R is 11 Are all hydrogen, R 10 is-CH 3 And R is 12 Are reactive groups as described above, preferably maleic anhydride. Maleic anhydride functionalized polypropylene gives excellent results.
Wherein the functionalized polyolefin comprises repeat units R PO1 And R is PO2 In some of the above embodiments of both, R PO2 And (R) PO1 +R PO1 ) Molar ratio (repeat unit R) PO1 Molar number of (d) per repeating unit R PO1 +R PO2 Molar number of (d) of 0.01From mol% to 6mol%, from 0.01mol% to 5.6mol%, or from 0.01mol% to 5mol%.
In a preferred embodiment, the functionalized polyolefin may be selected from the group consisting of functionalized polyethylene, functionalized polypropylene, functionalized polymethylpentene, functionalized polybutene-1, functionalized polyisobutene, functionalized ethylene propylene rubber and functionalized ethylene propylene diene monomer rubber, preferably the functionalized polyolefin polymer is functionalized polypropylene.
In some embodiments, the functionalized polyolefin has a melt mass flow rate ("MFR") of at least 1g/10min and/or an MFR of no more than 120g/10 min. In some embodiments, the functionalized polyolefin has an MFR of from 5g/10min to 100g/10min, or 10g/10min, from 80g/10min, or from 15g/10min to 70g/10 min. The MFR can be measured according to ASTM D1238 at 190℃and 1.2 kg.
In some embodiments, the functionalized polyolefin concentration in the polymer composition is at most 20 weight percent ("wt.%), at most 17wt.%, or at most 15 wt.%; and/or at least 1wt.%, or at least 2.5wt.%, or at least 5wt.%. In some embodiments, the concentration of functionalized polyolefin in the polymer composition is from 1wt.% to 20wt.%, or from 2wt.% to 17wt.%, or from 2wt.% to 15wt.%, or from 2.5wt.% to 15wt.%, or from 5wt.% to 15wt.%, or from 2.5wt.% to 10wt.%. As used herein, the weight percent of functionalized polyolefin is relative to the total weight of the polymer composition unless explicitly indicated otherwise.
In some embodiments, the polymer composition comprises a plurality of different functionalized polyolefins according to the above description, and the total concentration of these different functionalized polyolefins is within the ranges described above.
One of ordinary skill in the art will recognize that the choice of functionalized polyolefin concentration and polyamide concentration as described herein is related to the polyolefin weight ratio. The functionalized polyolefin concentration and the polyamide concentration are selected such that the polyolefin weight ratio is within a selected range and such that the total concentration of the one or more functionalized polyolefins, the polyphthalamide, and optionally the one or more other polyamides, the glass fibers, any optional reinforcing agents (e.g., glass spheres or carbon fibers), and optional additives in the polymer composition is less than or equal to 100wt.%.
Glass fiber
The polymer composition further comprises at least one glass fiber. Glass fibers are silica-based glass compounds containing several metal oxides that can be tailored to produce different types of glass. The primary oxide is silica in the form of silica sand; other oxides (such as calcium, sodium and aluminum) are incorporated to lower the melting temperature and to hinder crystallization.
The glass fibers may be continuous fibers or chopped glass fibers.
In some embodiments, the glass fibers have an average length of 3mm to 50 mm. In some such embodiments, the glass fibers have an average length of 3mm to 10mm, 3mm to 8mm, 3mm to 6mm, or 3mm to 5 mm. In alternative embodiments, the glass fibers have an average length of 10mm to 50mm, 10mm to 45mm, 10mm to 35mm, 10mm to 30mm, 10mm to 25mm, or 15mm to 25 mm.
In some embodiments, the glass fibers generally have an equivalent diameter of 5 to 20 μm, preferably 5 to 15 μm and more preferably 5 to 10 μm.
All glass fiber types may be used, such as A, C, D, E, M, S, R, T glass fibers (as described in Additives for Plastics Handbook [ handbook of plastic additives ], 2 nd edition, chapter 5.2.3 of John Murphy, pages 43-48), or any mixtures thereof or mixtures thereof.
E. R, S and T glass fibers are well known in the art. They are notably described in Fiberglass and Glass Technology [ glass fibers and glass technology ]]Wallenberger, frederick t.; bingham, paul A. (editions), 2010, XIV, chapter 5, pages 197-225. R, S and T glass fibers consist essentially of oxides of silicon, aluminum and magnesium. In particular, those glass fibers typically contain 62 to 75wt.% SiO 2 16-28wt.% Al 2 O 3 And 5 to 14wt.% MgO. In addition, R, S and T glass fibers comprise less than 10wt.% CaO.
In some embodiments, the glass fibers are high modulus glass fibers. The high modulus glass fiber has an elastic modulus of at least 76, preferably at least 78, more preferably at least 80, and most preferably at least 82GPa as measured according to ASTM D2343. Examples of high modulus glass fibers include, but are not limited to S, R and T glass fibers. A commercially available source of high modulus glass fibers is S-1 and S-2 glass fibers from Taishan corporation (Taishan) and AGY corporation, respectively.
In some embodiments, the glass fibers are low D k Glass fibers. Low D k The glass fibers have a dielectric constant of 4.0 to 5.5, 4.0 to 5.4, 4.0 to 5.3, 4.0 to 5.2, 4.0 to 5.1, or 4.0 to 5.0 at frequencies of 1MHz, 600MHz, 1GHz, and 2.4 GHz. Low D k The glass fibers may also have a low D f ("Low D) k /D f Glass fiber "). Such glass fibers have a D of 0.0005 to 0.001 at 1MHz, 1GHz, 600MHz, and 2.4GHz frequencies f . D of glass fibers f And D k Can be measured according to ASTM D150 (1.0 MHz) and ASTM D2520 (600 MHz, 1.0GHz and 2.4 GHz).
In some embodiments, the glass fibers are high modulus and low D k Is a glass fiber of (a).
In some embodiments, the glass fiber may have a dielectric constant of 4.0 to 5.5 at a frequency of 1MHz, measured according to ASTM D150, and/or a tensile modulus of at least 76GPa, as measured according to ASTM D2343.
The morphology of the glass fiber is not particularly limited. As noted above, the glass fibers may have a circular cross-section ("round glass fibers") or a non-circular cross-section ("flat glass fibers"). Examples of suitable flat glass fibers include, but are not limited to, glass fibers having oval, elliptical, and rectangular cross-sections.
In some embodiments wherein the polymer composition comprises flat glass fibers, the flat glass fibers have a cross-sectional longest diameter of at least 15 μm, preferably at least 20 μm, more preferably at least 22 μm, still more preferably at least 25 μm. Additionally or alternatively, in some embodiments, the flat glass fibers have a cross-sectional longest diameter of at most 40 μm, preferably at most 35 μm, more preferably at most 32 μm, still more preferably at most 30 μm. In some embodiments, the flat glass fibers have a cross-sectional diameter in the range of 15 to 35 μm, preferably 20 to 30 μm, and more preferably 25 to 29 μm. In some embodiments, the flat glass fibers have a cross-sectional shortest diameter of at least 4 μm, preferably at least 5 μm, more preferably at least 6 μm, still more preferably at least 7 μm. Additionally or alternatively, in some embodiments, the flat glass fibers have a cross-sectional shortest diameter of at most 25 μm, preferably at most 20 μm, more preferably at most 17 μm, still more preferably at most 15 μm. In some embodiments, the flat glass fibers have a cross-sectional shortest diameter in the range of 5 to 20, preferably 5 to 15, and more preferably 7 to 11 μm.
In some embodiments, the flat glass fibers have an aspect ratio (aspect ratio) of at least 2, preferably at least 2.2, more preferably at least 2.4, still more preferably at least 3. Aspect ratio is defined as the ratio of the longest diameter in a cross section of a glass fiber to the shortest diameter in the same cross section. Additionally or alternatively, in some embodiments, the flat glass fibers have an aspect ratio of at most 8, preferably at most 6, more preferably at most 4. In some embodiments, the flat glass fibers have an aspect ratio of 2 to 6, and preferably 2.2 to 4.
In some embodiments, wherein the glass fibers are round glass fibers, the glass fibers have an aspect ratio of less than 2, preferably less than 1.5, more preferably less than 1.2, even more preferably less than 1.1, most preferably less than 1.05. Of course, one of ordinary skill in the art will appreciate that the aspect ratio, by definition, cannot be less than 1, regardless of the morphology (e.g., round or flat) of the glass fibers.
In some embodiments, the glass fiber content in the polymer composition is at least 15wt.%, or at least 20wt.%, or at least 25wt.%, or at least 30wt.%. Additionally or alternatively, in some embodiments, the glass fiber content in the polymer composition is no more than 60wt.%, or no more than 55wt.%, or no more than 50wt.%, or no more than 45wt.%. In some embodiments, the glass fiber content in the polymer composition is 15wt.% to 60wt.%, or 20wt.% to 60wt.%, or 25wt.% to 60wt.%, or 30wt.% to 60wt.%, or 20wt.% to 55wt.%, or 25wt.% to 55wt.%, or 30wt.% to 55wt.%, or 20wt.% to 50wt.%, or 25wt.% to 50wt.%, or 30wt.% to 45wt.%. As used herein, the weight content (wt.%) of glass fibers is relative to the total weight of the polymer composition, unless explicitly indicated otherwise.
Optional reinforcing agent
The polymer composition may also comprise at least one reinforcing agent other than glass fibers as described above.
A large number of selected reinforcing agents (also referred to as reinforcing fibers or reinforcing fillers) may be added to the polymer composition according to the invention. They may be selected from fibrous reinforcing agents and particulate reinforcing agents.
The reinforcing agent may be selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), carbon fibers, synthetic polymer fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, wollastonite, glass beads (e.g., hollow glass beads or microspheres), and different types of glass fibers, i.e., different from the glass fibers used in the polymer composition according to the invention.
Fibrous reinforcing fillers are considered herein to be materials having a length, a width, and a thickness, wherein the average length is significantly greater than both the width and the thickness. Generally, such materials have an aspect ratio (defined as the average ratio between length and the largest of width and thickness) of at least 5, at least 10, at least 20, or at least 50. In some embodiments, the reinforcing fibers (e.g., carbon fibers) have an average length of 3mm to 50 mm. In an alternative embodiment, the reinforcing fibers have an average length of 10mm to 50 mm. The average length of the reinforcing fibers may be taken as the average length of the reinforcing fibers prior to incorporation into the polymer composition, or may be taken as the average length of the reinforcing fibers in the polymer composition.
The particulate reinforcing agent may be selected from mineral fillers (e.g. talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate) or glass beads (e.g. hollow glass beads or microspheres).
The reinforcing agent may be present in the composition in a total amount of at least 5wt.%, or at least 10wt.%, or at least 15wt.%, or at least 20wt.%, or at least 25wt.%, and/or at most 50wt.%, or at most 45wt.% based on the total weight of the polymer composition. The reinforcing agent may be present in the polymer composition, for example, in an amount ranging between 5 and 50wt.%, for example between 5 and 15wt.%, or between 10 and 50wt.%, between 20 and 50wt.%, or between 25 and 45wt.%, based on the total weight of the polymer composition.
In some embodiments, the polymer composition comprising glass fibers does not comprise a reinforcing agent other than the glass fibers.
In some embodiments, the polymer composition does not comprise glass spheres or beads, and in particular does not comprise hollow glass beads or microspheres.
Optional additives
In some embodiments, the polymer composition optionally comprises an additive selected from the group consisting of: toughening agents, plasticizers, light stabilizers, ultraviolet ("UV") stabilizers, heat stabilizers, pigments, dyes, antistatic agents, flame retardants, impact modifiers, lubricants, nucleating agents, antioxidants, processing aids, and any combination of one or more thereof. In some embodiments in which the polymer composition comprises optional additives, the total concentration of additives is no more than 15wt.%, no more than 10wt.%, no more than 5wt.%, no more than 1wt.%, no more than 0.5wt.%, no more than 0.4wt.%, no more than 0.3wt.%, no more than 0.2wt.%, or no more than 0.1wt.%, based on the total weight of the polymer composition.
Preparation of Polymer compositions
The present invention further relates to a process for preparing a polymer composition as detailed above, said process comprising melt blending: selected from polyamides having a C/amide molar ratio of greater than 8, functionalized polyolefins, glass fibers, optional reinforcing agents other than the glass fibers, any optional one or more other polyamides, and any other optional additives such as lubricants, UV stabilizers, heat stabilizers, impact modifiers, and the like.
In the context of the present invention, any melt blending method may be used to mix the polymeric and non-polymeric ingredients.
For example, the polymer component (e.g., the at least one polyphthalamide having a C/amide molar ratio of greater than 8 and the functionalized polyolefin) and one or more non-polymer components (e.g., the glass fibers) may be fed into a melt mixer (e.g., a single or twin screw extruder, a stirrer, a single or twin screw kneader, or a Banbury (Banbury) mixer), and the step of adding may be a single addition or a stepwise addition of all components in batches. When the polymeric component and the non-polymeric component are added stepwise in batches, a portion of these polymeric components and/or the one or more non-polymeric components are first added and then melt mixed with the remaining polymeric components and/or the remaining non-polymeric components added subsequently until a well-mixed composition is obtained.
If the glass fibers or the optional reinforcing agent exhibit a long physical shape (e.g., long or 'continuous' fibers), then stretch extrusion molding, pultrusion forming long fiber pellets, or pultrusion forming unidirectional materials may be used to prepare the reinforced composition.
Article and use
Another aspect of the invention provides the use of the polymer composition in an article.
It may be desirable to incorporate the polymer composition into an article, preferably a shaped article.
The article of manufacture may notably be used in mobile electronics, LED packages, electrical and electronic components (including but not limited to power unit components for computing, data systems and office equipment, and surface mount technology compatible connectors and contacts), medical device components; and electrical protection devices for miniature circuit breakers, contactors, switches and sockets), automotive components, and aerospace components (including but not limited to cabin interior components).
The polymer compositions described herein may be desirably integrated into mobile electronic device components due, at least in part, to their unexpectedly improved acid resistance while having excellent dielectric and mechanical properties.
The polymer composition may have a D measured according to ASTM D2520 of no more than 3.5, or no more than 3.4, or no more than 3.3, or no more than 3.25, or no more than 3.22, or no more than 3.2, or no more than 3.18, or no more than 3.15, or no more than 3.10 at 2.45GHz k And/or a D measured according to ASTM D2520 of at most 0.015, or at most 0.014, or at most 0.013, or at most 0.012, or at most 0.011, or at most 0.010, or at most 0.009, or at most 0.0087, or at most 0.0085, or at most 0.0082, or at most 0.008 at 2.45GHz f 。
The polymer composition is particularly useful in applications (e.g., antenna windows) in which the composition is overmolded onto a metal substrate that is subsequently anodized.
The term "mobile electronic device" is intended to mean an electronic device designed to be convenient for transportation and for use in different locations. Representative examples of mobile electronic devices may be selected from the group consisting of: mobile electronic telephones, personal digital assistants, notebook computers, tablet computers, radios, cameras and camera accessories, wearable computing devices (e.g., smart watches, smart glasses, etc.), calculators, music players, global positioning system receivers, portable game consoles and host accessories, hard disk drives, and other electronic storage devices.
Preferred mobile electronic devices include notebook computers, tablet computers, mobile electronic telephones, and wearable computing devices, such as watches.
The components of the mobile electronic device contemplated herein include, but are not limited to, antenna windows, accessories, snap-in parts, mutually movable parts, functional elements, operating elements, tracking elements, adjustment elements, carrier elements, frame elements, switches, connectors, cables, housings, and any other structural parts other than housings as used in mobile electronic devices, such as speaker parts, for example. In some embodiments, the device component may be a mounting component with mounting holes or other fastening means, including but not limited to a snap-fit connector between itself and another component of the mobile electronic device, including but not limited to a circuit board, microphone, speaker, display, battery, cover, housing, electrical or electronic connector, hinge, radio antenna, switch or switch pad.
In some embodiments, the mobile electronic device may be at least part of an input device.
In some embodiments, the mobile electronic device component may also be a mobile electronic device housing. "mobile electronic device housing" refers to one or more of the back cover, front cover, antenna housing, frame, and/or backbone of a mobile electronic device. The housing may be a single article or comprise two or more parts. "backbone" refers to the structural component on which the other components of the device are mounted, such as electronics, microprocessors, screens, keyboards, and keypads, antennas, battery receptacles, etc. The skeleton may be an internal component that is not visible or only partially visible from the exterior of the mobile electronic device. The housing may provide protection for the internal components of the device from impact from environmental factors (e.g., liquids, dust, etc.), as well as contamination and/or damage. Housing components such as covers may also provide substantial or primary structural support as well as impact protection for certain components (e.g., screen and/or antenna) that are exposed to the exterior of the device.
In some embodiments, the mobile electronic device housing is selected from the group consisting of: a mobile phone housing, an antenna housing, a tablet housing, a notebook housing, a tablet housing, or a watch housing.
In some embodiments, the mobile electronic device component may include, for example, a radio antenna. In this case, the radio antenna may be a WiFi antenna or an RFID antenna. In some such embodiments, at least a portion of the radio antenna is disposed on the polymer composition. Additionally or alternatively, at least a portion of the radio antenna may be removable from the polymer composition.
Examples of automotive components include, but are not limited to, components in automotive electronics, automotive lighting components (including, but not limited to, motor end caps, sensors, ECU housings, spools and solenoids, connectors, circuit protection/relays, actuator housings, li-ion battery systems, and fuse boxes), traction motors and power electronics (including, but not limited to, battery packs), electrical battery housings.
The article may be molded from the polymer composition by any method suitable for thermoplastics (e.g., extrusion, injection molding, blow molding, rotational molding, or compression molding).
The article may comprise a polymeric part over-molded onto a metal part, wherein the polymeric part contains or is made from the polymeric composition.
Preferred formation of the mobile electronic device component includes suitable melt processing methods such as injection molding or extrusion molding of the polymer composition, injection molding being the preferred molding method.
Use of polymer compositions or articles
In some embodiments, the polymer composition or article may be used to manufacture a mobile electronic device component as described above.
In particular, the use of the polymer composition may be particularly suitable for mobile electronic device components (e.g., antenna windows) in which the composition is applied to a metal substrate that is subsequently anodized.
The use may include first overmolding, injection molding or transfer molding a polymer composition according to the invention onto a metal substrate to form an assembly, and then subjecting the assembly to anodic oxidation.
The metal substrate may be formed of suitable materials including, but not limited to, aluminum, 5052 aluminum, and/or aluminum alloys.
For example, the polymer composition may be insert molded or over molded onto aluminum parts to form parts of a mobile device. Components comprising metal substrates may be anodized using an anodizing agent including, but not limited to, chromic acid, phosphoric acid, sulfuric acid, oxalic acid, and/or boric acid. The particular anodizing agent and conditions used depend on the specific details of the application, such as, for example, the type of metal being anodized.
Examples
The invention will now be described with reference to the following examples, which are intended to be illustrative only and are not intended to limit the scope of the invention. These examples demonstrate the acid resistance, dielectric properties and mechanical properties of the polymer compositions. As used in the examples, "E" represents an example embodiment of the present invention, and "CE" represents a counterexample.
Raw materials
Polyamide (PA)
In the examples, polyamides PA-1 to PA-9 listed in Table 1 were used. The polymer composition comprising POf and a polyamide selected from PA-1 to PA-3 is according to the invention, whereas the composition comprising a polyamide selected from PA-4 to PA-9 is the opposite.
TABLE 1
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Functionalized polyolefin ("PO) f ”)
Maleated polypropylene ("MA-PP"): from ExxonMobil under the trade namePO 1015 commercially available maleic anhydride functionalized polypropylene copolymer
Glass fiber ("GF")
Glass fiber ("GF 1"): low D commercially available as CPIC CS (HL) 301HP from Chongqing International composite company (Chongqing Polycomp International Corp.) k /D f Round glass fiber
Glass fiber ("GF 2"): e-glass round glass fibers commercially available as Nippon Electric Glass HP 3610
Glass fiber ("GF 3"): s-1 glass round glass fibers commercially available as Taishan S-1 HM435TM-10-3.0
Additive package
0.1g/100g of calcium stearate (as lubricant) as Ceasit I from BAERlocher Luo He company (Baerlocher) +0.2 g/100g from Basoff corporation (BASF corporation)B1171 (as heat stabilizer) +0.3 g/100g Chimassorb 944LD (as UV stabilizer) from basf company-total: 0.6wt.%
Optional colorant (typically 0.3 wt.%)
Compounding process
Will contain Polyamide (PA), functionalized polyolefin (PO f ) Glass Fiber (GF) and a composition comprising a lubricant (Ceasit I), a UV stabilizer (Chimassorb 944 LD) and a heat stabilizerB1171 The mixture of additive packages was melt blended in the amounts set forth in tables 2-7 below. The melt blending is used->ZSK-26 is co-rotating twin screw extruder and is subsequently molded according to ASTM D3641.
Test method
·D k And D f Measured at 2.45GHz according to ASTM D2520. D (D) k And D f Is performed on injection molded rectangular bars having dimensions of 3.2mm thickness by 12.7mm width by 125mm length.
Tensile modulus, strength and strain were measured on 5 injection molded ASTM type I tensile bars (165 mm overall length, 50mm gauge length, 12.7mm test section width, 3.2mm thickness) using a test speed of 0.2in/min according to ASTM D638 to measure tensile properties.
Flexural modulus was measured on 5 injection molded rectangular bars having dimensions of 3.2mm thickness by 12.7mm width by 125mm length.
ASTM notched izod impact test (value measured in ft-lb/in) was also performed according to ASTM D256 using 5 injection molded rectangular bars having dimensions of 3.2mm thickness by 12.7mm width by 125mm length.
ISO unnotched Izod test (in kJ/m 2 Measured in units) can alternatively be determined using ISO 180 using 10 injection molded ISO 1A type sticks (80±2mm in length, 10±0.2mm in width, 4±0.2mm in thickness).
Qualitative acid resistance:
the molded test specimens, typically ASTM type I tensile bars, are immersed in 1N sulfuric acid, 5N sulfuric acid and 5N nitric acid solutions at 80 ℃ for 4hr. Color change was measured using a spectrophotometer before and after acid treatment, and Δe was passed only for samples immersed in 1N sulfuric acid 94 (CIE 94) quantization is performed. The following visual evaluations were performed on the samples immersed in 1N sulfuric acid, 5N sulfuric acid, and 5N nitric acid. The test specimens were visually evaluated to determine whether surface defects (light or white specks, light or white streaks, surface roughening, and/or other aesthetic defects that were discernible to the naked eye) were formed. Surface defects are classified as 'none', 'tiny', or 'severe' respectively, depending on whether a single defect or a combination of defects occurs. In addition, the samples were visually evaluated to determine if dimensional changes, i.e., swelling, occurred during the acid exposure. Dimensional changes are classified as 'none', 'tiny', or 'severe' depending on the severity observed, i.e., 'tiny' will be classified as some slight swelling while maintaining the overall dimensional ratio of the part without warping at the part edges, while 'severe' will be classified as more severe swelling with changes in overall dimensional ratio, such as part edge warping.
Sample parameters are provided in tables 2-7, wherein:
“PO f the weight ratio "means the ratio value:
wherein W is PO And W is PA PO in the samples respectively f And the weight of PA. For comparison purposes, the PO in these examples f The weight ratio is calculated based on the weight of polyamide used in each blend, whether or not the polyamide is of the type>Polyphthalamide with a C/amide molar ratio of 8.
Example 1
This example demonstrates a specific pa+po f Improved dielectric properties, improved tensile elongation and improved unnotched izod (impact resistance) of the blend.
Samples E1, E2, E3, CE4, CE6 contain:
10wt.% of maleated polypropylene (MA-PP) to achieve 14.4% PO in each blend f Weight ratio;
30wt.% low D k Round glass fibers;
0.6wt.% additive package; and
the remaining wt.% comes from a semiaromatic polyamide selected from the group consisting of PA10, T/10, I (PA-1), PA10, T (PA-2), PA9, T (PA-3), PA6T/6I (PA-4) or PAMDX6 (PA-6) having a C/amide ratio of 9, 8.5, 7 and 7, respectively.
Samples CE1, CE2, CE3, CE4 and CE6 are similar to samples E1, E2, E3, CE4, CE6 except that they do not contain maleated polypropylene.
Sample CE5 contained 10wt.% of maleated polypropylene (MA-PP) to achieve 14.4% PO in the blend f Weight ratio; 30wt.% low D k Round glass fibers; 0.6wt.% of an additive package; and the remaining weight is aliphatic polyamide (PA-5): PA6,10, wherein the C/amide ratio is 8. Sample CE5 was similar to sample CE5 except that it did not contain maleated polypropylene.
The results are shown in tables 2 and 3.
CE1, CE2, CE3, CE4 and CE6, relative to the samples without MA-PP, wherein PO f Samples E1, E2, E3, CE4 and CE6 with a weight ratio of 14.4% of semi-aromatic polyamide and MA-PP improved unnotched izod (improvement from 36% to 106%)) Also, the tensile elongation (from 21% to 44%) was improved, and the dielectric properties (D k And D f Both).
In relation to sample CE5 without MA-PP, wherein PO f Sample CE5 with aliphatic polyamide (C/amide=8) and containing MA-PP in a weight ratio of 14.4% improved the dielectric properties (D k And D f Both), however, tensile elongation and unnotched izod were not improved.
It is also noted that the blends in Table 2 containing polyamides with a C/amide ratio greater than 8 (with or without MA-PP) have significantly improved acid resistance, whereas the polyamides in Table 3 with a C/amide ratio less than or equal to 8 have poor acid resistance, especially against nitric acid.
The improved acid resistance of the blends in table 2 consists of a low Δe indicating minimal color shift 94 Value (ΔE)<1, preferably +.0.28), no surface defects and no dimensional changes. In contrast, the poor acid resistance of the blends in Table 3 consisted of a generally higher ΔE 94 Value [(s) ]>0.28, sometimes>1) As well as the occurrence of minor and severe surface defects. The blends in table 3 still show satisfactory dimensional stability.
TABLE 2
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TABLE 3 Table 3
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Example 2
This example demonstrates a low D k Round glass fibers and various POs f Specific pa+po weight ratio f Improved dielectric properties, improved tensile elongation and improved unnotched izod (impact resistance) of the blend.
Sample E1 b 、E1 c 、E1 d The method comprises the following steps:
maleated polypropylene (MA-PP) in amounts of 2.5wt.%, 5wt.% and 7.5wt.% to achieve 3.7%, 7.8%, and 12.1% PO in the blend, respectively f Weight ratio;
30wt.% low D k Round glass fibers;
0.6wt.% additive package; and
residual weight% from semiaromatic polyamide (PA-1): PA10, T/10, I, wherein the C/amide ratio is 9.
Sample E1 in Table 4 b (PO f 3.7% by weight), E1 c (PO f 7.8% by weight) and E1 d (PO f 12.1% by weight) with sample CE1 (no MA-PP) and sample E1 (PO) previously described in example 1 f Weight ratio of 14.4%) was compared.
As shown in Table 4, dielectric D at 2.45GHz k And D f The values (ASTM D2520) are all with 14.4% PO into PA-1 f The weight ratio is reduced by adding MA-PP.
In addition, the tensile elongation of blends of PA10, T/10, I (PA-1) and MA-PP was a function of PO f The weight ratio increased steadily from 3.7% to 14.4%.
Sample E1 was obtained in the PA-1/MA-PP blend as compared to sample CE1 without MA-PP b 、E1 c 、E1 d 0 to 14.4% of each PO in E1 f The ratio by weight of unnotched izod impact values as shown in figure 1 with PO f The weight ratio increases steadily until the PO f The weight ratio was 12.7% (corresponding to +107% increase (compared to CE 1)) and tended to be smooth.
As plotted against sample CE without MA-PP1 in PA-1/MA-PP blend sample E1 b 、E1 c 、E1 d 0 to 14.4% of each PO in E1 f Dielectric constant D at 2.45GHz k D as shown in FIG. 2 of values k Along with PO f The weight ratio is steadily decreased by increasing.
TABLE 4 Table 4
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nd: not measured
Example 3
This example demonstrates a specific pa+po with E-glass round fibers f Improved dielectric properties, improved tensile elongation and improved unnotched izod (impact resistance) of the blend.
Sample E7 contains:
maleated polypropylene (MA-PP) in an amount of 10wt.% to achieve 14.4% PO f Weight ratio;
30wt.% E-glass round fibers;
0.6wt.% additive package; and
residual weight% from semiaromatic polyamide (PA-1): PA10, T/10, I, wherein the C/amide ratio is 9.
Sample CE7 is similar to sample E7 except that it does not contain maleated polypropylene.
The test results are shown in table 5.
As noted in Table 5, using E-glass fiber, sample E7 (PO f Weight ratio=14.4%) and the tensile elongation increased.
However, the relative improvement in tensile elongation (28% increase) observed for sample E7 using E-glass round fibers is not as good as for example 1 with the same PO f The weight ratio is lowD k Sample E1 of round glass fiber obtained (44% increase) was good.
In addition, sample E7 (PO) f Weight ratio = 14.4%; e-glass round fibers) was improved over that obtained without MA-PP in sample CE 7.
However, the relative improvement in unnotched izod value (60% increase) observed for sample E7 using E-glass round fibers is not as good as for example 1 with the same PO f Low D is used in weight ratio k Sample E1 of round glass fiber obtained (106% increase) was good.
TABLE 5
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nd: not measured
Example 4
This example demonstrates a specific pa+po using high modulus glass fiber (S-1 glass) f Improved dielectric properties, improved tensile elongation and improved unnotched izod values of the blends.
Sample E8 contains:
maleated polypropylene (MA-PP) in an amount of 10wt.% to achieve 14.4% PO in the blend f Weight ratio;
30wt.% of S1-glass round fibers;
0.6wt.% additive package; and
residual weight% from semiaromatic polyamide (PA-1): PA10, T/10, I, wherein the C/amide ratio is 9.
Sample CE8 is similar to sample E8 except that it does not contain maleated polypropylene.
The test results are shown in table 6.
TABLE 6
nd: not measured
As can be seen from Table 6, S1-glass round fibers, PO was used in sample E8 f The ISO unnotched izod impact value in the case of =14.4% was again improved (+60%) compared to that obtained in the case of no MA-PP in CE 8.
For sample E8 (PO f =14.4%; the improvement observed in ISO unnotched izod value (60% increase) for S1-glass round fibers) was compared with that observed with sample E7 (PO f =14.4%; e-glass round fibers) was comparable to the improvement (60%) in ASTM unnotched izod impact values.
Furthermore, the relative unnotched Izod impact improvement (60% increase) observed with sample E8 with S1-glass round fibers is not as good as with low D with the same polyamide PA-1 in example 1 k The round glass fiber obtained (106% increase) in sample E1 of the PA-1/MA-PP blend was good.
For sample E8 (PO f =14.4%; the improvement observed for the tensile elongation values of S1-glass round fibers (23% increase) was slightly less than with sample E7 (PO) f =14.4%; the improvement observed for E-glass round fibers (28% increase).
Furthermore, the improvement observed for the tensile elongation values of sample E8 with S1-glass round fibers (23%) is not as good as with the low D of the same polyamide PA-1 in example 1 k The round glass fiber obtained (44% increase) in the PA-1/MA-PP blend sample E1.
Example 5
Samples CE9, CE10, CE11 contain:
10wt.% of maleated polypropylene (MA-PP) to achieve 14.4% PO in the blend f Weight ratio;
30wt.% low D k Round glass fibers;
0.6wt.% additive package; and
the remaining wt% is derived from a semiaromatic polyamide (PA-7): PAPXD10, or aliphatic polyamide: PA10,10 (PA-8) and PA12 (PA-9), wherein the C/amide ratio is 9, 10 and 12, respectively.
Samples CE9, CE10 and CE11 are similar to samples CE9, CE10, CE11 except that they do not contain maleated polypropylene.
As shown in table 7, with 14.4% PO f Samples CE9, CE10, and CE11 in weight ratio, dielectric D at 2.45GHz k And D f The values all decrease with the addition of MA-PP.
From Table 7, it is observed that low Dk glass round fibers, PO, were used in sample CE9 f ASTM notched izod impact and tensile elongation were again improved in the case of =14.4% compared to that obtained in the absence of MA-PP in CE9 (40% and 25% improvement, respectively).
On the other hand, low Dk glass round fibers, PO, were used in sample CE10 × f ASTM notched izod impact and tensile elongation with =14.4% were not improved or slightly improved (0% and 8% improvement, respectively) compared to that obtained without MA-PP in CE 10.
TABLE 7
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The blends CE11, CE11 (with or without MA-PP) in table 7 containing an aliphatic polyamide (PA 12) with a C/amide ratio of 12 have improved acid resistance in 5N nitric acid, whereas the blends CE5, CE9, CE10 containing an aliphatic polyamide with a C/amide ratio of 8 to 10 have poor acid resistance in 5N nitric acid. However, blend C11 with PA12 had much poorer properties in terms of mechanical properties than blend CE5, CE 10. Use of low D in sample CE11 × k Glass round fiber, PO f ＝14.The unnotched Izod impact (according to ASTM D256) and tensile elongation at 4% were not improved over that obtained without MA-PP in CE11, with about a 30% loss of both properties.
Enhancement of tensile elongation and impact properties, in particular notched Izod, and dielectric properties (D k And D f ) Is reduced.
It is also noted that the blends in table 7 containing aliphatic polyamides with a C/amide ratio greater than 8 (C/amide ratio 10, 12), with or without MA-PP, have improved acid resistance in 5N sulfuric acid compared to the blends CE5, CE5 of table 3 containing aliphatic polyamides with a C/amide ratio less than or equal to 8.
While some improvement in mechanical properties was observed, the polymer compositions in tables 3 and 7 containing semi-aromatic polyamides other than polyphthalamides (MXD 6, PXD 10), polyphthalamides having a C/amide molar ratio of 7 (at most 8) (PA 6T/6I), and aliphatic polyamides (PA 6,10; PA10,10; PA 12) (regardless of their C/amide ratio) showed poorer acid resistance properties than the polymer compositions in tables 2 and 4 containing polyphthalamides having a C/amide molar ratio of greater than 8 (PA 10, T/10, I; PA10, T; PA9, T).
Thus, specific polyphthalamides (PA 10, T/10, I; PA10, T; PA9, T) exhibit a greatly reduced change in appearance after exposure to acidic media. The data show that the carbon to amide ratio (C/CONH) can play a role in acid resistance, particularly in 1N and 5N sulfuric acid, such that polyphthalamides wherein the C/amide molar ratio is greater than 8 exhibit better acid resistance than aliphatic polyamides and semiaromatic polyamides including polyphthalamides wherein the C/amide ratio is less than or equal to 8. The aromaticity of polyamides does not seem to be a factor in maintaining the appearance after acid exposure, i.e., semiaromatic polyamides and aliphatic polyamides in which the C/amide ratio is less than or equal to 8 all exhibit a different degree of defect formation in the appearance.
Overall, in the above examples, significant improvements in tensile elongation and impact properties (unnotched izod) were observed while allowing limited changes in appearance and limited dimensional changes after acid exposure. In addition, after incorporation of MA-PP into polyphthalamides (PA 10, T/10, I; PA10, T; PA9, T) having a molar ratio of C/amide of greater than 8, dielectric properties (D k And D f ) And (3) lowering.
While the preferred embodiments of the present invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit or teaching of the invention. The embodiments described herein are exemplary only and are not limiting. Many variations and modifications of the composition, article, and method are possible and are within the scope of the invention. The scope of protection is therefore not limited by the description set out above, but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each of the claims is incorporated into this specification as an embodiment of the invention. Thus, the claims are a further description and are an addition to the preferred embodiments of the present invention. The incorporation of any reference by reference of documents above is limited such that no subject matter is incorporated that is contrary to the explicit disclosure herein.
Claims (15)
1. A polymer composition comprising:
-a functionalized polyolefin,
a polyamide selected from polyphthalamides having a carbon to amide molar ratio of greater than 8,
glass fiber, and
functionalized Polyolefin (PO) f ) The weight ratio is greater than 0% and at most 27%,
wherein the method comprises the steps of
-the PO f The weight ratio is given by:and is also provided with
-W PA And W is PO The weight of the polyamide and the functionalized polyolefin in the polymer composition, respectively;
wherein the method comprises the steps of
The functionalized polyolefin comprises recurring units R respectively represented by the formula PO1 And R is PO2 ：
Wherein R is 5 To R 8 Independently selected from the group consisting of: hydrogen and formula
-(CH 2 ) m -CH 3 Alkyl represented, wherein m is an integer from 0 to 5; r is R 9 To R 12 Independently selected from the group consisting of: hydrogen, from- (CH) 2 ) m’ -CH 3 Alkyl groups represented, wherein m is an integer from 0 to 5, and reactive groups reactive with amine or carboxylic acid groups of the polyamide; and wherein R is 9 To R 12 At least one of which is a reactive group, and
the functionalized polyolefin comprises from 0.05 to 1.5mol% of recurring units R PO2 。
2. The polymer composition of claim 1, wherein the functionalized polyolefin is selected from the group consisting of functionalized polyethylene, functionalized polypropylene, functionalized polymethylpentene, functionalized polybutene-1, functionalized polyisobutylene, functionalized ethylene propylene rubber and functionalized ethylene propylene diene monomer rubber, preferably the functionalized polyolefin polymer is functionalized polypropylene.
3. The polymer composition of any of claims 1 or 2, wherein the functionalized polyolefin is functionalized with a reactive group selected from the group consisting of maleic anhydride, epoxide, isocyanate, and acrylic acid, preferably the reactive group is maleic anhydride.
4. A polymer composition according to any one of claims 1 to 3, which does not comprise:
semi-aromatic polyamides or polyphthalamides obtained by polycondensation between a diacid and a diamine monomer, one of which is aliphatic and has 6 or less carbon atoms; and/or
Polyphthalamides having a C/amide molar ratio of at most 8; and/or
Semi-aromatic polyamides other than polyphthalamides; and/or
-aliphatic polyamide; and/or
Any polyamide having a number average molecular weight of less than 1600.
5. The polymer composition of any one of claims 1 to 4, wherein the polyamide is at least one polyphthalamide having a carbon to amide molar ratio of at least 8.1, or at least 8.2, or at least 8.3, or at least 8.4, or at least 8.5, or at least 9.
6. The polymer composition of any one of claims 1 to 4, wherein the polyamide is a polyphthalamide selected from the group consisting of: PA10, T/10, I; PA10, T; PA9, T; and any combination thereof.
7. The polymer composition of any of claims 1 to 6, wherein the functionalized polyolefin is polypropylene functionalized with maleic anhydride as a reactive group.
8. The polymer composition of any one of claims 1 to 7, wherein the glass fiber has a dielectric constant of 4.0 to 5.5 at a frequency of 1MHz measured according to ASTM D150 and/or has a tensile modulus of at least 76GPa as measured according to ASTM D2343.
9. The polymer composition of any one of claims 1 to 8, wherein the glass fiber concentration in the polymer composition is 20wt.% to 60wt.%, preferably 25wt.% to 55wt.%, more preferably 30wt.% to 50wt.% based on the total weight of the polymer composition.
10. The polymer composition of any one of claims 1 to 9, wherein the functionalized polyolefin concentration in the polymer composition is 2wt.% to 20wt.%, preferably 2.5wt.% to 15wt.% based on the total weight of the polymer composition.
11. The polymer composition of any one of claims 1 to 10, wherein the polyamide concentration in the polymer composition is 40wt.% to 78wt.%, preferably 45wt.% to 77wt.%, more preferably 50wt.% to 70wt.% based on the total weight of the polymer composition.
12. The polymer composition of any of claims 1 to 11, wherein the polymer composition has a D measured according to ASTM D2520 of no more than 3.18, preferably no more than 3.15, more preferably no more than 3.10 at 2.45GHz k And/or D at 2.45GHz of at most 0.009 measured according to ASTM D2520 f 。
13. The polymer composition of any one of claims 1 to 12, wherein the PO in the polymer composition f The weight ratio is 2% to 25%, preferably 3% to 15%.
14. A mobile electronic device component comprising the polymer composition of any one of claims 1 to 13, preferably the mobile electronic device component is an antenna such as a mobile electronic antenna, an antenna window, an antenna housing or a mobile electronic housing.
15. A method for manufacturing a mobile electronic device component, the method comprising:
the polymer composition of any one of claims 1 to 13 is first overmolded, injection molded or transfer molded onto a metal substrate to form an assembly, and then the assembly is subjected to anodic oxidation.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202163152392P | 2021-02-23 | 2021-02-23 | |
| US63/152392 | 2021-02-23 | ||
| EP21182545.0 | 2021-06-29 | ||
| PCT/EP2022/054428 WO2022180051A1 (en) | 2021-02-23 | 2022-02-22 | Polyamide compositions with functionalized polyolefin and mobile electronic device components containing them |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116997611A true CN116997611A (en) | 2023-11-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280022371.2A Pending CN116997611A (en) | 2021-02-23 | 2022-02-22 | Polyamide compositions with functionalized polyolefins and mobile electronic device components containing them |
Country Status (1)
| Country | Link |
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| CN (1) | CN116997611A (en) |
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- 2022-02-22 CN CN202280022371.2A patent/CN116997611A/en active Pending
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