CN117098808A - Thermoplastic resin composition and molded article - Google Patents
Thermoplastic resin composition and molded article Download PDFInfo
- Publication number
- CN117098808A CN117098808A CN202280021454.XA CN202280021454A CN117098808A CN 117098808 A CN117098808 A CN 117098808A CN 202280021454 A CN202280021454 A CN 202280021454A CN 117098808 A CN117098808 A CN 117098808A
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- CN
- China
- Prior art keywords
- resin composition
- weight
- thermoplastic resin
- ltoreq
- molded article
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 95
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 93
- 229920000728 polyester Polymers 0.000 claims abstract description 13
- -1 polybutylene terephthalate Polymers 0.000 claims description 67
- 229920005989 resin Polymers 0.000 claims description 51
- 239000011347 resin Substances 0.000 claims description 51
- 230000003014 reinforcing effect Effects 0.000 claims description 44
- 239000002699 waste material Substances 0.000 claims description 43
- 239000000835 fiber Substances 0.000 claims description 39
- 229920001225 polyester resin Polymers 0.000 claims description 36
- 239000004645 polyester resin Substances 0.000 claims description 36
- 229920000578 graft copolymer Polymers 0.000 claims description 33
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 29
- 239000003365 glass fiber Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000945 filler Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 239000008188 pellet Substances 0.000 claims description 19
- 238000005259 measurement Methods 0.000 claims description 17
- ACYXOHNDKRVKLH-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile prop-2-enoic acid Chemical compound OC(=O)C=C.N#CC=CC=CC1=CC=CC=C1 ACYXOHNDKRVKLH-UHFFFAOYSA-N 0.000 claims description 16
- 238000011033 desalting Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 12
- 229920000800 acrylic rubber Polymers 0.000 claims description 11
- 229920000058 polyacrylate Polymers 0.000 claims description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000292 calcium oxide Substances 0.000 claims description 10
- 235000012255 calcium oxide Nutrition 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- 239000002667 nucleating agent Substances 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000003063 flame retardant Substances 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 4
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- 239000004611 light stabiliser Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 14
- 238000005452 bending Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 24
- 229920001577 copolymer Polymers 0.000 description 17
- 229920000139 polyethylene terephthalate Polymers 0.000 description 17
- 239000005020 polyethylene terephthalate Substances 0.000 description 17
- 239000002245 particle Substances 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- 230000000704 physical effect Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000007720 emulsion polymerization reaction Methods 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 11
- 238000011049 filling Methods 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 230000000379 polymerizing effect Effects 0.000 description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 239000007822 coupling agent Substances 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000012662 bulk polymerization Methods 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 150000003112 potassium compounds Chemical class 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 150000003388 sodium compounds Chemical class 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- 230000002411 adverse Effects 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 239000012184 mineral wax Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000002296 dynamic light scattering Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 1
- KQJQPCJDKBKSLV-UHFFFAOYSA-N 1-bromo-3-ethenylbenzene Chemical compound BrC1=CC=CC(C=C)=C1 KQJQPCJDKBKSLV-UHFFFAOYSA-N 0.000 description 1
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- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
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- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- RLFXJQPKMZNLMP-UHFFFAOYSA-N 2-phenylprop-2-enenitrile Chemical compound N#CC(=C)C1=CC=CC=C1 RLFXJQPKMZNLMP-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
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- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
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- 239000004677 Nylon Substances 0.000 description 1
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- 241000269851 Sarda sarda Species 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241000269841 Thunnus albacares Species 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 238000005275 alloying Methods 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
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- 239000008121 dextrose Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 235000012438 extruded product Nutrition 0.000 description 1
- 229960001781 ferrous sulfate Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
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- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
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- 238000005809 transesterification reaction Methods 0.000 description 1
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present application relates to a thermoplastic resin composition and a molded article manufactured using the same. According to the present application, the present application has an effect of providing a thermoplastic resin composition having tensile strength, elongation and bending strength equal to or superior to those of a conventional polyester composite material, and a molded article manufactured using the same; has greatly improved impact strength, flexural modulus and heat distortion temperature under high load; and thus is suitable for lightweight automobile parts requiring high rigidity.
Description
Technical Field
Cross-reference to related applications
The present application claims priority from korean patent application No.10-2022-0011939 filed at 1 month 27 of 2022 by the korean intellectual property office and korean patent application No.10-2022-0184385 filed again at 12 months 26 of 2022 based on the priority of the above-mentioned patents, the disclosures of each of which are incorporated herein by reference.
The present application relates to a thermoplastic resin composition and a molded article manufactured using the same. More specifically, the present application relates to a thermoplastic resin composition having a tensile strength, elongation and bending strength equal to or higher than those of a conventional composite material composed of a polyester resin and a reinforcing resin; has greatly improved impact strength, flexural modulus and heat distortion temperature under high load; and thus is suitable for light-weight automobile parts requiring high heat resistance and high rigidity, and to a molded article manufactured using the thermoplastic resin composition.
Background
Research is actively being conducted on using a composite material prepared by alloying a polyester resin and a reinforcing resin for reinforcing rigidity such as impact strength as a material for automobile parts.
Examples of the reinforcing resin include acrylate-styrene-acrylonitrile graft copolymer, styrene-acrylonitrile copolymer, and polyethylene terephthalate, which have excellent mechanical strength, moldability, and long-term properties.
On the other hand, a technique for obtaining a polyester resin by recovering a waste fishing net has been developed. For example, in the case of fishing tuna, ultra-large fishing nets are used to catch bonito and yellow fin tuna, and the estimated amount of waste fishing nets thrown into the sea each year is about 640,000 tons.
Oversized nets for tuna fishing have a length of 2km and a width of 80m, weigh about 60 tons, and are typically made of nylon and polyethylene terephthalate.
Accordingly, when the above composite material is prepared using a large waste fishing net and high heat resistance, high rigidity and weight saving are achieved, an environmentally friendly composite material capable of preventing environmental pollution can be provided.
[ related art literature ]
[ patent literature ]
KR 2019-0027115 A
Disclosure of Invention
Technical problem
Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a thermoplastic resin composition having tensile strength, elongation and bending strength equal to or better than those of conventional polyester composites; has greatly improved impact strength, flexural modulus and heat distortion temperature under high load; and thus is suitable for light-weight automobile parts requiring high heat resistance and high rigidity, and a molded article manufactured using the thermoplastic resin composition.
The above and other objects can be accomplished by the present invention as hereinafter described.
Technical proposal
According to an aspect of the present invention, there is provided a thermoplastic resin composition comprising:
polyester resins, reinforcing resins, filling fibers and recycled molded articles,
wherein 37.ltoreq.a.ltoreq.59.2, 15.ltoreq.b.ltoreq.19.9, 20.ltoreq.c.ltoreq.34.9 and 5.ltoreq.d.ltoreq.14.9 are satisfied simultaneously when the weight of the polyester resin is a, the weight of the reinforcing resin is b, the weight of the filler fiber is c and the weight of the recovered molded article is d,
the recovered molded article is a product obtained by processing a waste fishing net.
The polyester resin may be polybutylene terephthalate having an Intrinsic Viscosity (IV) of less than 1.0 dl/g.
The reinforcing resin may comprise a styrene-acrylonitrile copolymer and an acrylate-styrene-acrylonitrile graft copolymer in a weight ratio of 1:0.5 to 5.
The styrene-acrylonitrile copolymer may comprise 66 to 76% by weight of an aromatic vinyl compound and 26 to 34% by weight of a vinyl cyanide compound.
The acrylate-styrene-acrylonitrile graft copolymer may comprise 40 to 47 wt% of an acrylic rubber, 30 to 37 wt% of an aromatic vinyl compound, and 23 to 28 wt% of a vinyl cyanide compound.
The filler fibers may be glass fibers comprising 45 to 55 weight percent silica, 15 to 32 weight percent alumina, and 15 to 32 weight percent calcium oxide.
The product obtained by processing the waste fishing net may be a product obtained by desalting and sheet-forming waste fishing net pellets containing Ca, fe and S in total in an amount of 60 to 99.9 wt% and Na, mg, al, si, K, ti, ni, zn, sb and Cl in total in an amount of 0.1 to 40 wt% based on 100 wt% of the inorganic component measured using an ICP-OES apparatus.
The product obtained by processing the waste fishing net may be a product obtained by precutting a waste fishing net made of polyethylene terephthalate having an Intrinsic Viscosity (IV) of 0.6dl/g to 0.9dl/g, removing sand and salt therefrom, and cutting, desalting and extruding the waste fishing net.
The thermoplastic resin composition may contain one or more additives selected from the group consisting of antioxidants, lubricants, hydrolysis inhibitors, flame retardants, nucleating agents, heat stabilizers, light stabilizers, and thickeners.
The thermoplastic resin composition may have a flexural modulus of 8,000mpa or more, as measured according to standard measurement ISO 178 at a rate of 2mm/min and a span of 64 (span).
The thermoplastic resin composition may have a weight of 7.0kJ/m as measured according to Standard measurement ISO 180/1A 2 The above room temperature impact strength.
The thermoplastic resin composition may have a heat distortion temperature of 180 ℃ or more, as measured according to standard measurement ISO 75 at 1.80 MPa.
According to another aspect of the present invention, there is provided a method for preparing a thermoplastic resin composition, comprising:
desalting a waste polyester fishing net having an Intrinsic Viscosity (IV) of 0.6dl/g to 0.9dl/g to obtain waste fishing net pellets and subjecting the waste fishing net pellets to sheet molding to manufacture a recovered molded article comprising a total of 60 to 99.9 wt% of Ca, fe and S and a total of 0.1 to 40 wt% of Na, mg, al, si, K, ti, ni, zn, sb and Cl based on a total of 100 wt% of an inorganic component measured using ICP-OES equipment; and
Melt kneading and extruding the recovered molded article, a polyester resin having an Intrinsic Viscosity (IV) of less than 1.0dl/g, a reinforcing resin and a filler fiber,
wherein 37.ltoreq.a.ltoreq.59.2, 15.ltoreq.b.ltoreq.19.9, 20.ltoreq.c.ltoreq.34.9, and 5.ltoreq.d.ltoreq.14.9 are satisfied simultaneously when the weight of the polyester resin is a, the weight of the reinforcing resin is b, the weight of the filler fiber is c, and the weight of the recovered molded article is d.
According to still another aspect of the present invention, there is provided a molded article manufactured using the above thermoplastic resin composition.
The molded article may be an automotive part, and may include a LAMP (LAMP) bracket or an electronic control unit power pack (ECU Powerpack) bracket.
Advantageous effects
According to the present invention, the present invention has an effect of providing a thermoplastic resin composition having tensile strength, elongation and bending strength equal to or superior to those of a conventional polyester composite material, and a molded article manufactured using the same; has greatly improved impact strength, flexural modulus and heat distortion temperature under high load; and thus is suitable for lightweight automobile parts requiring high heat resistance and high rigidity.
Accordingly, the thermoplastic resin composition according to the present invention can be used for manufacturing automobile parts. In particular, the thermoplastic resin composition according to the present invention can be used for manufacturing lightweight automobile parts requiring high heat resistance and high rigidity, such as lamp brackets and ECU power pack brackets.
Drawings
Fig. 1 is a flow chart illustrating a process of processing a waste fishing net to obtain a waste fishing net product, which is used in one embodiment described later.
Fig. 2 includes an image (a) of a fishing net (before use), an image (b) of a waste fishing net (after use), and an image (C) of a waste fishing net product obtained according to the process of fig. 1.
Detailed Description
Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.
The terms and words used in the present specification and the appended claims should not be construed as limited to general or dictionary meanings, but should be construed as having meanings and concepts matching the technical concept of the present invention in order to describe the present invention in the best mode.
In the present specification, a polymer containing a specific compound means a polymer prepared by polymerizing the compound, and units in the polymer are derived from the compound.
The present inventors confirmed that when a polyester composite material composed of a polyester resin and a reinforcing resin, a filler fiber, and a recovered molded article obtained by desalting a waste fishing net are contained, a thermoplastic resin composition having tensile strength, elongation, and bending strength equal to or superior to those of a conventional polyester composite material is prepared; has greatly improved impact strength, flexural modulus and heat distortion temperature under high load; and thus is suitable for lightweight automobile parts requiring high heat resistance and high rigidity. Based on these results, the present inventors have conducted further studies to complete the present invention.
In the present disclosure, the composition ratio of the (co) polymer may refer to the content of units constituting the (co) polymer, or may refer to the content of units added during the polymerization of the (co) polymer.
In this disclosure, "content" refers to weight unless otherwise defined.
The thermoplastic resin composition of the present invention comprises a polyester resin, a reinforcing resin, a filler fiber and a recovered molded article, wherein when the weight of the polyester resin is a, the weight of the reinforcing resin is b, the weight of the filler fiber is c and the weight of the recovered molded article is d, 37.ltoreq.a.ltoreq.59.2, 15.ltoreq.b.ltoreq.19.9, 20.ltoreq.c.ltoreq.34.9 and 5.ltoreq.d.ltoreq.14.9 are satisfied at the same time, and the recovered molded article is a product obtained by processing a waste fishing net. In this case, the present invention has an effect of providing a thermoplastic resin composition having a tensile strength, elongation and bending strength equal to or superior to those of conventional polyester composites; has greatly improved impact strength, flexural modulus and heat distortion temperature under high load; and thus is suitable for lightweight automobile parts requiring high heat resistance and high rigidity.
Further, the thermoplastic resin composition of the present invention comprises a polyester resin, a reinforcing resin, a filling fiber and a recovered molded article, wherein 37.ltoreq.a.ltoreq.59.2, 15.ltoreq.b.ltoreq.19.9, 20.ltoreq.c.ltoreq.34.9 and 5.ltoreq.d.ltoreq.14.9 are satisfied simultaneously when the weight of the polyester resin is a, the weight of the reinforcing resin is b, the weight of the filling fiber is c and the weight of the recovered molded article is d, and the recovered molded article is a product obtained by desalting and sheet-forming waste fishing net pellets containing, based on a total of 100 wt% of inorganic components, 60 wt% to 99.9 wt% of Ca, fe and S and 0.1 wt% to 40 wt% of Na, mg, al, si, K, ti, ni, zn, sb and Cl in total, measured using an ICP-OES apparatus. In this case, the present invention has an effect of providing a thermoplastic resin composition having a tensile strength, elongation and bending strength equal to or superior to those of conventional polyester composites; has greatly improved impact strength, flexural modulus and heat distortion temperature under high load; and thus is suitable for lightweight automobile parts requiring high heat resistance and high rigidity.
Further, the thermoplastic resin composition of the present invention comprises a polyester resin, a reinforcing resin, a filling fiber and a recovered molded article, wherein when the weight of the polyester resin is a, the weight of the reinforcing resin is b, the weight of the filling fiber is c and the weight of the recovered molded article is d, 37.ltoreq.a.ltoreq.59.2, 15.ltoreq.b.ltoreq.19.9, 20.ltoreq.c.ltoreq.34.9 and 5.ltoreq.d.ltoreq.14.9 are simultaneously satisfied, and the recovered molded article is a product obtained by precutting a waste fishing net made of polyethylene terephthalate having an Intrinsic Viscosity (IV) of 0.6dl/g to 0.9dl/g, removing sand and salt therefrom, and cutting, desalting and extruding the waste fishing net. In this case, the present invention has an effect of providing a thermoplastic resin composition having a tensile strength, elongation and bending strength equal to or superior to those of conventional polyester composites; has greatly improved impact strength, flexural modulus and heat distortion temperature under high load; and thus is suitable for lightweight automobile parts requiring high heat resistance and high rigidity.
In the following the description of the preferred embodiments, the respective components constituting the thermoplastic resin composition of the present invention are described in detail as follows.
Polyester resin
In one embodiment of the present invention, the polyester resin comprises polyalkylene terephthalate. In view of physical properties and cost, polybutylene terephthalate may be preferably used as the polyester resin.
Polybutylene terephthalate can be obtained by direct esterification of 1, 4-butanediol with terephthalic acid or dimethyl terephthalate, or by polycondensation after transesterification of 1, 4-butanediol with terephthalic acid or dimethyl terephthalate.
The polyester resin has an Intrinsic Viscosity (IV) measured according to ASTM D2857 of preferably 0.6dl/g to 0.9dl/g, more preferably 0.7dl/g to 0.9 dl/g. When the intrinsic viscosity of the polyester resin, particularly polybutylene terephthalate, is within this range, a thermoplastic resin composition having an excellent balance between mechanical properties and moldability can be obtained.
In the present disclosure, when measuring intrinsic viscosity, a sample solution having a concentration of 0.05g/ml was prepared by completely dissolving a sample in methylene chloride as a solvent, and then filtered using a filter to obtain a filtrate, unless otherwise specified. Then, using the obtained filtrate, intrinsic viscosity was measured at 20℃using an Ubbelohde viscometer.
Reinforced resin
The thermoplastic resin composition of the present invention may contain, as the reinforcing resin, an acrylate-styrene-acrylonitrile graft copolymer containing an acrylic rubber, an aromatic vinyl compound and a vinyl cyanide compound and a styrene-acrylonitrile copolymer containing an aromatic vinyl compound and an acrylonitrile monomer.
Acrylate-styrene-acrylonitrile graft copolymers
In one embodiment of the present invention, the acrylate-styrene-acrylonitrile graft copolymer may be prepared by graft polymerizing an acrylic rubber, an aromatic vinyl compound, and an acrylonitrile monomer. For example, the acrylate-styrene-acrylonitrile graft copolymer may be a graft copolymer comprising an acrylic rubber having an average particle diameter of 50nm to 500 nm. In this case, mechanical properties such as impact strength and tensile strength, heat resistance, coloring property, and weather resistance may be excellent.
For example, the acrylic rubber contained in the graft copolymer may have an average particle diameter of 50nm to 500nm, preferably 70nm to 450nm, more preferably 100nm to 350 nm. Within this range, mechanical properties and heat resistance may be excellent. When the average particle diameter of the acrylic rubber is smaller than this range, mechanical properties such as impact strength and tensile strength may be deteriorated. When the average particle diameter of the acrylic rubber exceeds this range, the heat stability may be lowered.
In the present disclosure, the average particle size may be measured by dynamic light scattering. Specifically, the average particle diameter of a sample in the form of latex can be measured in a gaussian mode using a particle size distribution analyzer (Nicomp 380). Further, the average particle diameter may be an arithmetic average particle diameter in a particle diameter distribution measured by dynamic light scattering, specifically, a scattering intensity average particle diameter.
As a specific measurement example, a sample was prepared by diluting 0.1g of latex (TSC: 35 wt% to 50 wt%) 1,000 to 5,000 times with distilled water, i.e., the sample was appropriately diluted so as not to deviate significantly from the intensity set point of 300kHz, and the sample was placed in a glass tube. Then, in a measurement mode of dynamic light scattering/intensity 300 kHz/intensity-weight gaussian analysis, the average particle diameter of the sample was measured using a flow cell in autodilution. At this time, the set values are as follows: temperature: 23 ℃; measurement wavelength: 632.8nm; channel width: 10 musec.
For example, the content of the acrylic rubber contained in the graft copolymer may be 40 to 47% by weight, preferably 40 to 45% by weight, more preferably 40 to 43% by weight, based on the total weight of the rubber polymer and the monomers constituting the graft copolymer. Within this range, weather resistance, impact strength, and scratch resistance may be excellent.
For example, the acrylic rubber may be prepared by emulsion polymerization of (meth) acrylate monomers. As a specific example, the acrylic rubber may be prepared by mixing a (meth) acrylic monomer, an emulsifier, an initiator, a grafting agent, a crosslinking agent, an electrolyte, and water and emulsion polymerizing the mixture. In this case, the grafting efficiency may be improved, and thus, physical properties such as impact resistance may be excellent.
For example, the (meth) acrylic acid ester monomer may contain one or more selected from alkyl (meth) acrylates having 2 to 8 carbon atoms, preferably alkyl acrylates having an alkyl group having 4 to 8 carbon atoms, more preferably butyl acrylate or ethylhexyl acrylate.
In the present disclosure, (meth) acrylate monomers include both acrylate monomers and methacrylate monomers.
The emulsion polymerization may be a graft emulsion polymerization, and may be carried out, for example, at 50 to 85 ℃, preferably 60 to 80 ℃.
The initiator is a free radical initiator. As specific examples, the initiator may include one or more selected from the group consisting of: inorganic peroxides including sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; organic peroxides including t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3, 5-trimethylhexanol peroxide, and t-butyl peroxyisobutyrate; and azo compounds including azobisisobutyronitrile, azobis-2, 4-dimethylvaleronitrile, azobis (cyclohexanecarbonylnitrile), and methyl azobisisobutyrate.
In addition to the initiator, an activator may be further added to promote the initiation reaction.
For example, the activator may comprise one or more selected from sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, anhydrous sodium pyrophosphate, and sodium sulfate.
For example, the initiator may be added in an amount of 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, more preferably 0.02 to 0.1 part by weight, based on 100 parts by weight in total of the rubber polymer and the monomer constituting the graft copolymer. Within this range, emulsion polymerization can be promoted, and the remaining amount of the initiator in the graft copolymer can be minimized to an amount of several tens ppm.
The weight of the rubber is based on solids in the case of latex, or may be the weight of monomer added when preparing the rubber according to another method.
For example, the emulsifier may comprise one or more selected from the group consisting of: a potassium compound of alkylbenzene sulfonate, a sodium compound of alkylbenzene sulfonate, a potassium compound of alkyl carboxylate, a sodium compound of alkyl carboxylate, a potassium compound of oleic acid, a sodium compound of oleic acid, a potassium compound of alkyl sulfate, a sodium compound of alkyl sulfate, a potassium compound of alkyl dicarboxylic acid salt, a sodium compound of alkyl dicarboxylic acid salt, a potassium compound of alkyl ether sulfonate, a sodium compound of alkyl ether sulfonate, and an ammonium compound of allyloxy nonylphenoxypropane-2-oxymethyl sulfonate, preferably sodium dodecylbenzene sulfonate.
As the emulsifier, a commercially available emulsifier can be used. In this case, one or more selected from SE10N, BC-10, BC-20, HS10, hitenol KH10 and PD-104 may be used.
For example, the emulsifier may be added in an amount of 0.15 to 2.0 parts by weight, preferably 0.3 to 1.5 parts by weight, more preferably 0.5 to 1.2 parts by weight, based on 100 parts by weight in total of the rubber polymer and the monomer constituting the graft copolymer. Within this range, emulsion polymerization can be promoted, and the remaining amount of the initiator in the graft copolymer can be minimized to an amount of several tens ppm.
When emulsion polymerization is carried out, a molecular weight regulator may be further added. For example, the molecular weight regulator may comprise one or more selected from the group consisting of tertiary dodecyl mercaptan, n-dodecyl mercaptan and alpha-methylstyrene dimer, preferably tertiary dodecyl mercaptan.
For example, the molecular weight regulator may be added in an amount of 0.1 to 1 part by weight, preferably 0.2 to 0.8 part by weight, more preferably 0.4 to 0.6 part by weight, based on 100 parts by weight in total of the rubber polymer and the monomer constituting the graft copolymer.
The emulsion polymerization may be initiated after the monomers are fed in batches to the reactor. Alternatively, some of the monomers may be fed into the reactor before the emulsion polymerization starts, and the remaining portion may be fed into the reactor in batches after the emulsion polymerization starts, or the emulsion polymerization may be performed while continuously feeding the monomers or gradually feeding the monomers for a certain period of time.
The resulting graft copolymer may be in the form of a latex and may be recovered in the form of a dry powder by aggregation, dewatering and drying processes.
As the coagulant for aggregation, salts such as calcium chloride, magnesium sulfate, and aluminum sulfate; acidic substances such as sulfuric acid, nitric acid, and hydrochloric acid; and mixtures thereof.
For example, the content of the aromatic vinyl compound contained in the graft copolymer may be 30 to 37% by weight, preferably 33 to 37% by weight, based on the total weight of the rubber polymer and the monomers constituting the graft copolymer. Within this range, mechanical properties such as tensile strength and impact strength, and processability may be excellent.
For example, the aromatic vinyl compound may contain one or more selected from styrene, α -methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, t-butylstyrene, o-bromostyrene, p-chlorostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene and vinylnaphthalene. In this case, processability may be excellent due to appropriate fluidity, and mechanical properties such as tensile strength and impact strength may be excellent.
The vinyl cyanide compound contained in the graft copolymer may contain one or more selected from acrylonitrile, methacrylonitrile, acetonitrile, phenylacrylonitrile, α -chloroacrylonitrile, preferably acrylonitrile.
For example, the vinyl cyanide compound may be contained in the graft copolymer in an amount of 23 to 28% by weight, preferably 23 to 26% by weight, more preferably 24 to 26% by weight, based on the total weight of the rubber polymer and the monomers constituting the graft copolymer. Within this range, impact resistance and processability may be excellent.
In the present disclosure, the term "total weight of the copolymer" may refer to the actual total weight of the resulting copolymer, or may refer to the total weight of rubber and/or monomer added in place of the copolymer.
Commercial products may be used as long as the product satisfies the definition of the graft copolymer of the present invention.
For example, the graft copolymer may have a weight average molecular weight of 40,000g/mol to 200,000g/mol, preferably 60,000g/mol to 190,000g/mol, more preferably 80,000g/mol to 190,000 g/mol. In this case, processability may be excellent due to appropriate fluidity, and mechanical properties such as tensile strength and impact strength may be excellent.
In the present disclosure, the weight average molecular weight may be measured by gel permeation chromatography (GPC, waters Breeze) using Tetrahydrofuran (THF) as an eluent. In this case, the weight average molecular weight is obtained as a relative value to a Polystyrene (PS) standard sample. Specifically, the weight average molecular weight is a weight average molecular weight (Mw) converted by gel permeation chromatography (GPC, PL GPC220, agilent Technologies) based on polystyrene.
Specifically, the polymer to be measured was dissolved in tetrahydrofuran to a concentration of 1%, and 10 μl of the dissolved sample was injected into a Gel Permeation Chromatograph (GPC) at a flow rate of 0.3 mL/min. At this time, analysis was performed at a sample concentration of 2.0mg/mL (100. Mu.l injection) at 30 ℃. In this case, two columns (PLmixed B, waters co.) were connected in series, and RI detector (2414,Agilent Waters Co) was used. At this point, measurements were made at 40 ℃ and the data were processed using ChemStation.
Styrene-acrylonitrile copolymer
In the present disclosure, a styrene-acrylonitrile copolymer constituting the reinforcing resin includes an aromatic vinyl compound and a vinyl cyanide compound.
The styrene-acrylonitrile copolymer can improve the balance of physical properties of the thermoplastic resin composition. That is, the styrene-acrylonitrile copolymer may act as a matrix resin to control surface impact, mechanical properties, processability, coating appearance, and to prevent cracking after coating.
The styrene-acrylonitrile copolymer can be prepared by copolymerizing an aromatic vinyl compound and a vinyl cyanide compound.
Specifically, the styrene-acrylonitrile copolymer may be prepared by adding the aromatic vinyl compound and the vinyl cyanide compound in portions or continuously and polymerizing these compounds using one or more methods selected from emulsion polymerization, suspension polymerization, and bulk polymerization.
The types of aromatic vinyl compounds and vinyl cyanide compounds are as described in the acrylate-styrene-acrylonitrile graft copolymers.
For example, the styrene-acrylonitrile copolymer may contain 66 to 76% by weight, preferably 68 to 74% by weight, more preferably 70 to 74% by weight of the aromatic vinyl compound based on 100% by weight of the total monomers constituting the copolymer. Within this range, the balance of physical properties and surface gloss of molded articles produced using the thermoplastic resin composition of the present invention can be further improved.
For example, the styrene-acrylonitrile copolymer may contain 26 to 34% by weight, preferably 26 to 32% by weight, more preferably 26 to 30% by weight of the vinyl cyanide compound based on 100% by weight of the total monomers constituting the copolymer. Within this range, the balance of physical properties and surface gloss of molded articles produced using the thermoplastic resin composition of the present invention can be further improved.
For example, the styrene-acrylonitrile copolymer may have a weight average molecular weight of 40,000g/mol to 200,000g/mol, preferably 60,000g/mol to 190,000g/mol, more preferably 80,000g/mol to 190,000 g/mol. Within this range, the balance of physical properties between mechanical properties, processability and coating appearance can be easily controlled.
Commercial products may be used as long as the product satisfies the definition of the styrene-acrylonitrile copolymer of the present invention.
The styrene-acrylonitrile copolymer may preferably comprise two or more copolymers containing different amounts of vinyl cyanide-based monomers.
That is, the styrene-acrylonitrile copolymer may comprise: a first copolymer comprising a first amount of a vinyl cyanide compound; and a second copolymer containing a second amount of a vinyl cyanide compound. In this case, the second content is greater than the first content.
For example, the first copolymer may comprise 21 to 31 wt% (corresponding to the first content) of the vinyl cyanide compound, and the second copolymer may comprise greater than 31 wt% and 35 wt% or less (corresponding to the second content) of the vinyl cyanide compound. Within this range, the mechanical properties and processability of molded articles produced by injecting the thermoplastic resin composition of the present invention can be further improved.
The styrene-acrylonitrile copolymer may be prepared by polymerizing an aromatic vinyl compound and a vinyl cyanide compound using one or more methods selected from the group consisting of bulk polymerization, emulsion polymerization, and suspension polymerization. When bulk polymerization is used, manufacturing costs can be reduced, and mechanical properties can be excellent.
When bulk polymerization is used, since additives such as an emulsifier and a suspending agent are not added, a high purity copolymer having a minimized amount of impurities can be prepared. Therefore, in order to prepare a thermoplastic resin composition capable of maintaining transparency, it is advantageous to include a copolymer prepared by bulk polymerization.
For example, bulk polymerization can be carried out by adding an additive containing a molecular weight regulator and a polymerization initiator to a monomer mixture, and then polymerizing the mixture, if necessary, with an organic solvent as a reaction medium.
As a specific example, the method of preparing the styrene-acrylonitrile copolymer may include the steps of: 100 parts by weight of a monomer mixture comprising an aromatic vinyl compound and a vinyl cyanide compound, 20 to 40 parts by weight of a reaction medium, and 0.05 to 0.5 parts by weight of a molecular weight regulator are mixed, and the reaction mixture is polymerized at a reaction temperature of 130 to 170 ℃ for 2 to 4 hours.
As the reaction medium, a solvent generally used in the art may be used without particular limitation. For example, the reaction medium may be an aromatic hydrocarbon such as ethylbenzene, benzene, toluene or xylene.
For example, the method for producing a styrene-acrylonitrile copolymer may be carried out using a continuous processor composed of a raw material input pump, a continuous stirring tank into which a reaction raw material is continuously fed, a preheating tank for preheating a polymer solution discharged from the continuous stirring tank, a volatilization tank for volatilizing unreacted monomers and/or a reaction medium, a polymer transfer pump, and an extruder for producing a polymer in pellet form.
For example, the extrusion process may be performed at 210 to 240 ℃, but the present invention is not limited thereto.
Commercial products may be used as long as the product satisfies the definition of the styrene-acrylonitrile copolymer of the present invention.
The reinforcing resin may comprise a styrene-acrylonitrile copolymer and an acrylate-styrene-acrylonitrile graft copolymer in a weight ratio of 1:0.5 to 5, 1:0.7 to 1.5, or 1:0.8 to 1.2. Within this range, a thermoplastic resin composition having an excellent balance among chemical resistance, mechanical properties and heat resistance can be obtained.
Filling fiber
In the present invention, filler fibers are included in order to improve mechanical properties, heat resistance and dimensional stability of the thermoplastic resin composition.
In one embodiment of the present invention, glass fibers comprising 45 to 55 wt% silica, 15 to 32 wt% alumina, and 15 to 32 wt% calcium oxide may be used as the filler fibers. When glass fibers satisfying the above ranges are used, a thermoplastic resin composition having an excellent balance among chemical resistance, mechanical properties and heat resistance can be obtained.
In one embodiment of the invention, the glass fiber comprises preferably 50 to 55 wt% silica, 15 to 27 wt% alumina and 15 to 25 wt% calcia, more preferably 51 to 53 wt% silica, 17 to 19 wt% alumina and 15 to 17 wt% calcia. In this case, a thermoplastic resin composition having an excellent balance of physical properties among processability, specific gravity and mechanical properties can be obtained, and a molded article having high heat resistance, high rigidity and high toughness can be produced using the thermoplastic resin composition.
The glass fibers of the present invention may have a circular cross-section or a flat cross-section. In this case, excellent rigidity and appearance can be ensured, and weight saving can be achieved.
For example, the glass fiber may have a fiber size of 1:1 to 1:4, as a specific example, 1:1 to 1:3, more specifically 1: aspect ratio of 1. Here, the aspect ratio is expressed as a ratio (L/D) of the length (L) to the diameter (D). Within this range, the thermoplastic resin composition of the present invention may have high rigidity and toughness, and may improve elongation and surface appearance thereof. As a specific example, the glass fiber may have a fiber size of 1:3 to 1:4, more specifically 1:4, aspect ratio of 4. Within this range, in addition to high rigidity and toughness, a product advantageous in terms of flatness, deformation, and orientation can be provided.
In the present disclosure, diameter and length may be measured using Scanning Electron Microscopy (SEM). Specifically, 20 inorganic fillers were selected using a scanning electron microscope, the diameter and length of each inorganic filler were measured using an icon bar (icon bar) capable of measuring a diameter, and then the average diameter and average length were calculated.
For example, the average diameter may be 10 μm to 13 μm, as a specific example, 10 μm to 11 μm, and the average length may be 2.5mm to 6mm, as a specific example, 3mm to 4mm. Within this range, the processability can be improved, and thus the tensile strength of a molded article produced by molding the thermoplastic resin composition of the present invention can be improved.
The glass fibers may have a circular, rectangular, oval, dumbbell, or diamond shape in cross-section.
In one embodiment of the invention, the glass fibers may be used in combination with other inorganic fibers and/or natural fibers, and the inorganic fibers may comprise carbon fibers, basalt fibers, and the natural fibers may comprise kenaf and hemp.
In one embodiment of the invention, the glass fibers may be treated with sizing agents, such as lubricants, coupling agents, and surfactants, during fiber manufacture or post-treatment.
The lubricant is mainly used for forming good strands when manufacturing glass fibers, and the coupling agent plays a role in enabling good adhesion between the glass fibers and the matrix resin. When the types of the matrix resin and the glass fiber are appropriately selected, excellent physical properties can be imparted to the thermoplastic resin composition.
The coupling agent may be applied directly to the glass fibers or added to the organic matrix. The content thereof may be appropriately selected in order to sufficiently exhibit the performance of the coupling agent.
Examples of the coupling agent include amine coupling agents, acrylic coupling agents, and silane coupling agents, with silane coupling agents being preferred.
As a specific example, the silane-based coupling agent may include γ -aminopropyl triethoxysilane, γ -aminopropyl trimethoxysilane, N- (β -aminoethyl) γ -aminopropyl triethoxysilane, γ -methacryloxypropyl triethoxysilane, γ -glycidoxypropyl trimethoxysilane, and β - (3, 4-epoxyethyl) γ -aminopropyl trimethoxysilane.
Recycled molded articles
In one embodiment of the present invention, the recycled molded article may include a product obtained by processing waste fishing net.
The waste fishing net may be a resin including polyamide and polyethylene terephthalate, and may include polyamide and a part of polyethylene terephthalate prepared by polycondensation of terephthalic acid and ethylene glycol, but the present invention is not limited thereto.
In this case, the polyamide may be contained in an amount of 3 to 48mol%, preferably 5 to 20mol%, based on the polyethylene terephthalate. When the polyamide is contained in an amount within this range, a thermoplastic resin composition having an excellent balance among surface smoothness, heat resistance and high rigidity can be obtained.
In one embodiment of the present invention, the polyamide-polyethylene terephthalate has an Intrinsic Viscosity (IV) measured according to ASTM D2857 of preferably 0.6dl/g to 0.9dl/g, more preferably 0.7dl/g to 0.9 dl/g. When the inherent viscosity of the polyamide-polyethylene terephthalate is within this range, a thermoplastic resin composition having an excellent balance among mechanical properties, moldability and high rigidity can be obtained.
In one embodiment of the present invention, for example, the recovered molded article may be black chips obtained by desalting waste fishing nets having a size of 2km×80m according to a process flow chart of fig. 1 described later. At this time, the size corresponds to the approximate size of a fishing net used in a tuna seine boat.
Fig. 1 is a process flow chart showing a process of manufacturing a recovered molded article used in one example described later.
According to FIG. 1 below, in step S1, a scrap fishing net (polyamide: 80% by weight, polyethylene terephthalate: 20% by weight) having a size of 2km×80m is precut using a cutter. The cutting size at the time of precutting is not particularly limited. Further, when used after cleaning about 200kg of waste fishing net, washing and desalting processes described later can be easily performed.
Subsequently, in step S2, the pre-cut waste fishing net is put into an industrial washer and washed for about 5 to 15 hours to primarily remove salt while removing sand.
In step S3, the washed waste fishing net is put into a centrifugal separator equipped with blades, cut into a size of 5cm to 15cm, and desalted.
Then, in step S4, extrusion is performed at a temperature ranging from 200 ℃ to 270 ℃, and granulation is performed to manufacture chips.
The inorganic materials contained in the resulting recovered molded articles were analyzed using an ICP-OES apparatus, and the results are shown in table 1 below.
TABLE 1
As shown in table 1, the product obtained by processing the waste fishing net may be an extruded product obtained by desalting and sheet-forming the waste fishing net pellets containing Ca, fe and S in total of 60 to 99.9 wt%, preferably 60 to 90 wt%, more preferably 60 to 80 wt%, and Na, mg, al, si, K, ti, ni, zn, sb and Cl in total of 0.1 to 40 wt%, preferably 10 to 40 wt%, more preferably 20 to 40 wt%, based on total of 100 wt% of the inorganic components, measured using ICP-OES equipment. Within the above range, a thermoplastic resin composition having an excellent balance between mechanical properties and moldability can be obtained.
Thermoplastic resin composition
In one embodiment of the present invention, the thermoplastic resin composition comprises the above polyester resin, a reinforcing resin, a filler fiber, and a recycled molded article. When the weight of the polyester resin is a, the weight of the reinforcing resin is b, the weight of the filler fiber is c, and the weight of the recovered molded article is d, it is preferable that 37.ltoreq.a.ltoreq.59.2, 15.ltoreq.b.ltoreq.19.9, 20.ltoreq.c.ltoreq.34.9, and 5.ltoreq.d.ltoreq.14.9 are satisfied at the same time. When the polyester resin, the reinforcing resin, the filler fiber and the recovered molded article are contained within the above-mentioned content ranges, a thermoplastic resin composition having an excellent balance between heat resistance and mechanical properties can be obtained.
Further, when the weight of the polyester resin is a, the weight of the reinforcing resin is b, the weight of the filling fiber is c, and the weight of the recovered molded article is d, it is preferable that 37.ltoreq.a.ltoreq.50, 15.ltoreq.b.ltoreq.18, 27.ltoreq.c.ltoreq.33, and 7.ltoreq.d.ltoreq.14 are satisfied at the same time. When the polyester resin, the reinforcing resin, the filling fiber, and the recovered molded article are contained in the above-mentioned content ranges, mechanical properties such as impact strength and tensile strength, heat resistance, scratch resistance, and coloring properties may be excellent, and the physical property balance and surface gloss of the molded article may be further improved.
Additive agent
In one embodiment of the present invention, the thermoplastic resin composition may contain one or more additives selected from the group consisting of antioxidants, lubricants, hydrolysis inhibitors, flame retardants, nucleating agents, heat stabilizers, light stabilizers, and thickeners.
For example, the antioxidant may comprise a phenolic antioxidant, a phosphorous antioxidant, or both. In this case, thermal oxidation may be prevented during the extrusion process, and mechanical properties may be excellent.
The lubricant according to the invention may be a lignite derived mineral wax or an olefinic wax. In this case, the releasability and injectability of the thermoplastic resin composition can be maintained at excellent levels.
The olefinic wax may be a polymer having a low melt viscosity and may be an oily solid having sliding properties and plasticity. For example, the olefin-based wax may contain at least one selected from polyethylene wax and polypropylene wax, and commercially available olefin wax may be used.
The mineral wax has a high melting point, a high hardness, and a high thermal stability, and one or more selected from OP and E-grade mineral waxes may be used. In addition, a commercially available product may be used as long as the product satisfies the definition of the mineral wax of the present invention.
Various known hydrolysis inhibitors may be used as the hydrolysis inhibitor according to the present invention within a range that does not adversely affect the thermoplastic resin composition of the present invention. Representative commercially available hydrolysis inhibitors include phosphate compounds, such as those represented by the formula NaH 2 PO 4 Indicated as sodium dihydrogen phosphate.
Various known nucleating agents may be used as the nucleating agent according to the present invention within a range that does not adversely affect the thermoplastic resin composition of the present invention. Representative commercially available nucleating agents include BRUGGONE_P22.
Various known flame retardants may be used as the flame retardant according to the present invention within a range that does not adversely affect the thermoplastic resin composition of the present invention. Representative commercially available flame retardants include Clariant_Exolit-OP-1230.
Various known thickeners may be used as the thickener according to the present invention within a range that does not adversely affect the thermoplastic resin composition of the present invention. Representative commercial thickeners include Xibond250.
In one embodiment of the present invention, for example, the additive may be contained in an amount of 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the base resin. Within this range, excellent releasability and injectability can be achieved.
In addition, processing aids, pigments, colorants, and the like may be included as necessary.
In one embodiment of the present invention, the thermoplastic resin composition may have a flexural modulus of 8,000mpa or more, as a specific example, 8,000mpa to 8,900mpa, as measured according to standard measurement ISO 178 at a span of 64 and a rate of 2 mm/min. Within this range, the molding characteristics required for an injection product having high rigidity can be ensured.
For example, the thermoplastic resin composition according to the invention may have a molecular weight of 7.0kJ/m, as measured according to Standard measurement ISO 180/1A 2 Above, as a specific example, 7.0kJ/m 2 To 9.0kJ/m 2 Is a room temperature impact strength of (c). Within this range, the impact strength and appearance required for an injection product having high rigidity can be ensured.
In one embodiment of the present invention, for example, the thermoplastic resin composition may have a heat distortion temperature of 180 ℃ or more, as a specific example, 180 ℃ to 199 ℃ as measured under a high load of 1.80MPa according to standard measurement ISO 75. Within this range, high load-heat resistance characteristics required for high rigidity can be ensured.
The thermoplastic resin composition may have a room temperature tensile strength of 123MPa or more, as a specific example, 123MPa to 150MPa, as measured at a rate of 50mm/min according to standard measurement ISO 527. In this case, mechanical properties, in particular, rigidity and processability may be excellent.
The thermoplastic resin composition may have an elongation of 2.0% or more, as a specific example, 2.0% to 2.8%, as measured at a rate of 50mm/min according to standard measurement ISO 527. In this case, the molding characteristics required for an injection product having high rigidity can be ensured.
The thermoplastic resin composition may have a melt flow index (260 ℃,2.16 kg) of 12.0g/10min or more, as a specific example, 12.0g/10min to 15.0g/10min, as measured according to standard measurement ISO 1133. In this case, the processability may be excellent.
The thermoplastic resin composition may have a concentration of 1.44g/cm 3 Above, as a specific example, 1.44g/cm 3 To 1.48g/cm 3 Is a density of (3). In this case, the processability may be excellent.
As a specific example, the thermoplastic resin composition contains the above polyester resin, reinforcing resin, filler fiber, and recycled molded article. When the weight of the polyester resin is a, the weight of the reinforcing resin is b, the weight of the filler fiber is c, and the weight of the recovered molded article is d, 40.2.ltoreq.a.ltoreq.43.2, 15.ltoreq.b.ltoreq.17, 27.ltoreq.c.ltoreq.32, and 6.5.ltoreq.d.ltoreq.10 are satisfied simultaneously. When the recovered molded article is a black chip obtained by desalting a waste fishing net having a size of 2km×80m and is a molded article obtained by desalting and sheet-forming a waste fishing net pellet containing Ca, fe and S in total of 60 to 99.9 wt% and Na, mg, al, si, K, ti, ni, zn, sb and Cl in total of 0.1 to 40 wt% based on 100 wt% of the total inorganic component as measured using ICP-OES equipment, a thermoplastic resin composition can be provided: has a tensile strength, elongation and flexural strength equal to or better than conventional polyester composites; has greatly improved impact strength, flexural modulus and heat distortion temperature under high load; and thus is suitable for lightweight automobile parts requiring high rigidity.
Method for producing thermoplastic resin composition
The thermoplastic resin composition according to the present invention may be prepared by methods known in the art. For example, the thermoplastic resin composition in the form of pellets may be prepared by a method of melt-extruding a mixture of components and additives using an extruder, and injection molded articles and extrusion molded articles may be manufactured using the pellets.
The method for producing a thermoplastic resin composition shares all technical features of the thermoplastic resin composition described above. Therefore, a repetitive description thereof will be omitted.
In one embodiment of the invention, the pellets are extruded at a temperature of 200 ℃ to 270 ℃ or 230 ℃ to 260 ℃. At this time, the temperature refers to the cylinder temperature.
The extrusion kneader commonly used in the art to which the present invention pertains may be used without particular limitation, and a twin-screw extrusion kneader is preferably used.
During injection, the mold temperature is 90 ℃ to 150 ℃, preferably 100 ℃ to 120 ℃. When the mold temperature is lower than 90 ℃, the appearance may deteriorate, and the influence of improving crystallinity and physical properties due to annealing may be insignificant. When the mold temperature exceeds 150 ℃, the pellets adhere to the mold, decreasing the mold release and increasing the cooling rate. In addition, in terms of mass production, productivity may be greatly reduced.
For example, the injection process may be performed using an injection molding machine in which the hopper temperature and the nozzle temperature are set to 290 ℃ to 305 ℃, respectively.
For example, the method of producing a thermoplastic resin composition of the present invention comprises: a step of desalting the waste fishing net to obtain black polyamide-polyethylene terephthalate chips; and a step of melt-kneading and extruding a resin composition comprising a matrix resin containing polyamide-polyethylene terephthalate and polybutylene terephthalate, a reinforcing resin, glass fibers, and an additive.
As a specific example, the method of preparing the thermoplastic resin composition may include the steps of: desalting a waste polyester fishing net having an Intrinsic Viscosity (IV) of 0.6dl/g to 0.9dl/g to obtain waste fishing net pellets and subjecting the waste fishing net pellets to sheet forming to produce a recovered molded article comprising a total of 60 to 99.9 wt% Ca, fe and S and a total of 0.1 to 40 wt% Na, mg, al, si, K, ti, ni, zn, sb and Cl based on a total of 100 wt% of inorganic components as measured using ICP-OES equipment; and a step of melt-kneading and extruding the recovered molded article, a polyester resin having an Intrinsic Viscosity (IV) of less than 1.0dl/g, a reinforcing resin and a filler fiber.
When the weight of the polyester resin is a, the weight of the reinforcing resin is b, the weight of the filler fiber is c, and the weight of the recovered molded article is d, 37.ltoreq.a.ltoreq.59.2, 15.ltoreq.b.ltoreq.19.9, 20.ltoreq.c.ltoreq.34.9, and 5.ltoreq.d.ltoreq.14.9 can be satisfied at the same time.
As the filler fiber, a glass fiber containing 45 to 55% by weight of silica, 15 to 32% by weight of alumina, and 15 to 32% by weight of calcium oxide can be used.
Molded article
The thermoplastic resin composition of the present invention can be used as a material for molded articles requiring excellent moldability and heat resistance as well as high rigidity and toughness.
The thermoplastic resin composition of the present invention can be used for manufacturing light parts requiring high rigidity and toughness. For example, the thermoplastic resin composition may be used for manufacturing electric/electronic parts, parts for office equipment, in addition to automobile parts.
According to another embodiment of the present invention, there is provided a molded article manufactured using the above thermoplastic resin composition.
For example, the molded article may be a lightweight automobile part having high heat resistance and rigidity.
As another example, the molded article may be a lightweight automobile part having high heat resistance and rigidity, such as a lamp bracket or an ECU power pack bracket.
In describing the thermoplastic resin composition and the molded article, it should be noted that other conditions or apparatuses not explicitly described herein may be appropriately selected within the scope of the general practice in the art without particular limitation.
Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily practice the present invention. The invention may, however, be embodied in many different forms and is not limited to these embodiments. In this specification,% means% by weight unless otherwise defined.
Examples (example)
Polybutylene terephthalate, polyethylene terephthalate, recycled molded articles, reinforcing resins, filling fibers, antioxidants, nucleating agents and hydrolysis inhibitors used in examples and comparative examples of the present invention are as follows.
( A-1) polybutylene terephthalate (intrinsic viscosity (IV): 0.8dl/g )
( A-2) polybutylene terephthalate (intrinsic viscosity (IV): 1.0dl/g )
(B) Recovered molded article: the black chips of fig. 2C obtained by processing waste fishing net according to the process flow chart of fig. 1; intrinsic viscosity: 0.8dl/g
(C) Polyethylene terephthalate: polyethylene terephthalate homopolymer with an intrinsic viscosity of 0.8dl/g
(D) Reinforced resin
(D-1 a) acrylate-styrene-acrylonitrile graft copolymer: graft copolymer obtained by graft polymerizing 41% by weight of butyl acrylate rubber, 34% by weight of styrene and 25% by weight of acrylonitrile
(D-1 b) acrylate-styrene-acrylonitrile graft copolymer: graft copolymer obtained by graft polymerizing 45% by weight of butyl acrylate rubber, 35% by weight of styrene and 20% by weight of acrylonitrile
(D-2 a) styrene-acrylonitrile copolymer: copolymers obtained by polymerizing 72% by weight of styrene and 28% by weight of acrylonitrile (weight average molecular weight: 130,000 g/mol)
(D-2 b) styrene-acrylonitrile copolymer: copolymers obtained by polymerizing 76% by weight of styrene and 24% by weight of acrylonitrile (weight average molecular weight: 120,000 g/mol)
(E) Filling fiber
(E-1) glass fiber: glass fibers comprising 48% by weight of silica, 12% by weight of alumina, 35% by weight of calcium oxide and 5% by weight of other components comprising magnesium oxide (average length: 3mm, average particle size: 14 μm)
(E-2) glass fiber: glass fibers comprising 44 weight percent silica, 14 weight percent alumina, 36 weight percent calcia, and 6 weight percent other components (average length: 3mm, average particle size: 10 μm)
(E-3) glass fiber: glass fiber comprising 52% by weight of silica, 18% by weight of alumina, 16% by weight of calcium oxide and 14% by weight of other components comprising MgO (average length: 3mm, average particle size: 10 μm)
(additive)
-an antioxidant: pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate)
-a nucleating agent: polyethylene wax (LDPE wax)
Hydrolysis inhibitor: from chemical NaH 2 PO 4 Indicated sodium dihydrogen phosphate
Examples 1 to 3 and comparative examples 1 to 11
Each component was added according to the content described in tables 2 and 3 below, and melt-kneaded using a twin-screw extruder heated to 230 to 260 ℃ to prepare a resin composition in the form of pellets. For reference, the antioxidant was added in an amount of 0.4 wt%, the nucleating agent was added in an amount of 0.3 wt%, and the hydrolysis inhibitor was added in an amount of 0.1 wt%.
In tables 2 and 3, the weight of the polyester resin is represented by a, the weight of the reinforcing resin is represented by b, the weight of the filling fiber is represented by c, and the weight of the recovered molded article is represented by d. Here, b corresponds to the total amount of D-1a and D-2a in the reinforcing resin.
After the obtained pellets were dried at 120 ℃ for more than 4 hours, the dried pellets were injected using a screw type injection machine at a mold temperature of 120 ℃, a hopper temperature of 250 ℃ and a nozzle temperature of 260 ℃ to obtain samples for evaluating mechanical properties. For the prepared test pieces having a thickness of 4mm, a width of 10mm and a marked line segment of 50mm (elongation measurement), physical properties thereof were measured in the following manner, and the results are shown in tables 4 and 5 below.
* Melt flow index (g/10 min): melt flow index was measured at 260℃under a load of 2.16kg according to ISO 1133.
* Impact Strength (KJ/m) 2 ): impact strength was measured according to ISO 180/1A (notched, room temperature 23 ℃).
* Tensile strength (MPa) and elongation (%): tensile strength and elongation were measured according to ISO 527 at room temperature of 23℃and a rate of 50 mm/min.
* Flexural strength (MPa) and flexural modulus (MPa): flexural strength and flexural modulus were measured according to ISO 178 at a span of 64 and a rate of 2 mm/min.
* Heat distortion temperature (c): the heat distortion temperature is measured according to ISO 75 under a high load of 1.80 MPa.
* Density (g/cm) 3 ): the density was measured according to ISO 1183.
TABLE 2
| Classification | Example 1 | Example 2 | Example 3 |
| A-1 | 43.2 | 40.2 | 40.2 |
| A-2 | - | - | - |
| B | 10.0 | 13.0 | 6.5 |
| C | - | - | 6.5 |
| D-1a | 8.0 | 8.0 | 8.0 |
| D-1b | - | - | - |
| D-2a | 8.0 | 8.0 | 8.0 |
| D-2b | - | - | - |
| E-1 | - | - | - |
| E-2 | - | - | - |
| E-3 | 30.0 | 30.0 | 30.0 |
TABLE 3
TABLE 4
| Classification | Unit (B) | Example 1 | Example 2 | Example 3 |
| Melt flow index | g/10min | 13.0 | 15.0 | 14.0 |
| Impact strength of cantilever beam | kJ/m 2 | 8.5 | 8.5 | 8.5 |
| Tensile Strength | MPa | 141 | 140 | 143 |
| Elongation percentage | ％ | 2.3 | 2.0 | 2.0 |
| Flexural Strength | MPa | 190 | 189 | 190 |
| Flexural modulus | MPa | 8610 | 8600 | 8400 |
| Heat distortion temperature | ℃ | 185 | 182 | 186 |
| Density of | g/cm 3 | 1.46 | 1.46 | 1.46 |
TABLE 5
Examples 1 to 3 contain polybutylene terephthalate as an essential component of the present invention in a predetermined composition ratio as shown in tables 2 and 4,Recovered chips, reinforcing resin and glass fiber obtained by desalting waste fishing net, exhibited 7.0kJ/m 2 The cantilever impact strength of 140MPa or more, the tensile strength of 2.0% or more, the bending strength of 189MPa or more, the bending modulus of 8,600MPa or more, the heat distortion temperature of 182 ℃ or more and 1.46g/cm 3 Is a density of (3). Based on these results, it can be confirmed that examples 1 to 3 exhibit an excellent balance of physical properties between high rigidity, high load, heat resistance and specific gravity.
On the other hand, as shown in tables 3 and 5, in the case of comparative example 1 in which polybutylene terephthalate was contained in an amount smaller than the range of the present invention and the recovered molded article was contained in an amount exceeding the range of the present invention, the heat distortion temperature was reduced as compared with example 1.
Further, as shown in tables 3 and 5, in the case of comparative examples 2 and 3 in which silica, alumina and calcium oxide constituting the glass fiber were contained in amounts out of the scope of the present invention, flexural modulus and heat distortion temperature were reduced as compared with example 1.
Further, as shown in tables 3 and 5, in the case of comparative example 4 in which the intrinsic viscosity of polybutylene terephthalate is out of the range of the present invention, the flexural modulus and the fluidity are reduced as compared with example 1.
Further, as shown in tables 3 and 5, in the case of comparative example 5 in which the amount of the component constituting the acrylate-styrene-acrylonitrile graft copolymer in the reinforcing resin was out of the range of the present invention, the impact strength, the flexural modulus and the heat distortion temperature were lowered. In the case of comparative example 6 in which the amount of the component constituting the styrene-acrylonitrile copolymer in the reinforcing resin was out of the range of the present invention, the flexural modulus and the heat distortion temperature were poor, as compared with example 1.
Further, as shown in tables 3 and 5, in the case of comparative example 7 in which the acrylate-styrene-acrylonitrile copolymer was not contained in the reinforcing resin, the impact strength, the elongation and the density were poor. In the case of comparative example 8 in which the styrene-acrylonitrile copolymer was not contained in the reinforcing resin, elongation, flexural modulus and density were poor as compared with example 1.
Further, as shown in tables 3 and 5, in the case of comparative example 9 in which an excessive amount of the acrylate-styrene-acrylonitrile copolymer was contained in the reinforcing resin, the heat distortion temperature was poor, compared with example 1.
Further, as shown in tables 3 and 5, in the case of comparative example 10 containing the recovered molded article in an amount smaller than the range of the present invention, mechanical properties such as tensile strength, bending strength and bending modulus difference were compared with example 1.
Further, as shown in tables 3 and 5, in the case of comparative example 11 comprising polyethylene terephthalate homopolymer instead of recycled molded article, the melt flow index, flexural modulus and heat distortion temperature were reduced as compared with example 1.
In summary, when the recovered molded article satisfying the specific physical properties described in the present invention is mixed with the polyester resin, the reinforcing resin and the filler fiber in an appropriate content ratio, high heat resistance and high rigidity can be obtained while satisfying environmental friendliness, as compared with a thermoplastic resin composition comprising a conventional polyester composite material containing fresh polyethylene terephthalate instead of the recovered molded article.
Claims (14)
1. A thermoplastic resin composition comprising a polyester resin, a reinforcing resin, a filler fiber and a recycled molded article,
wherein 37.ltoreq.a.ltoreq.59.2, 15.ltoreq.b.ltoreq.19.9, 20.ltoreq.c.ltoreq.34.9, and 5.ltoreq.d.ltoreq.14.9 are satisfied simultaneously when the weight of the polyester resin is a, the weight of the reinforcing resin is b, the weight of the filler fiber is c, and the weight of the recovered molded article is d,
the recovered molded article is a product obtained by processing a waste fishing net.
2. The thermoplastic resin composition of claim 1, wherein said polyester resin is polybutylene terephthalate having an Intrinsic Viscosity (IV) of less than 1.0 dl/g.
3. The thermoplastic resin composition of claim 1, wherein said reinforcing resin comprises a styrene-acrylonitrile copolymer and an acrylate-styrene-acrylonitrile graft copolymer in a weight ratio of 1:0.5 to 5.
4. The thermoplastic resin composition of claim 3, wherein said styrene-acrylonitrile copolymer comprises 66 to 76 weight percent of an aromatic vinyl compound and 26 to 34 weight percent of a vinyl cyanide compound.
5. The thermoplastic resin composition of claim 3, wherein said acrylate-styrene-acrylonitrile graft copolymer comprises 40 to 47 weight percent of an acrylic rubber, 30 to 37 weight percent of an aromatic vinyl compound, and 23 to 28 weight percent of a vinyl cyanide compound.
6. The thermoplastic resin composition of claim 1, wherein said filler fibers are glass fibers comprising 45 to 55 weight percent silica, 15 to 32 weight percent alumina, and 15 to 32 weight percent calcia.
7. The thermoplastic resin composition of claim 1, wherein the product obtained by processing the waste fishing net is a product obtained by desalting and sheet-forming waste fishing net pellets containing Ca, fe and S in total in an amount of 60 to 99.9 wt% and Na, mg, al, si, K, ti, ni, zn, sb and Cl in total in an amount of 0.1 to 40 wt%, based on total 100 wt% of inorganic components, measured using ICP-OES equipment.
8. The thermoplastic resin composition of claim 1, wherein said thermoplastic resin composition comprises one or more additives selected from the group consisting of antioxidants, lubricants, hydrolysis inhibitors, flame retardants, nucleating agents, heat stabilizers, light stabilizers, and thickeners.
9. The thermoplastic resin composition of claim 1, wherein said thermoplastic resin composition has a flexural modulus of 8,000mpa or greater, as measured according to standard measurement ISO 178 at a rate of 2mm/min and a span of 64.
10. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a weight of 7.0kJ/m as measured according to standard measurement ISO 180/1A 2 The above room temperature impact strength.
11. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a heat distortion temperature of 180 ℃ or greater as measured according to standard measurement ISO 75 at 1.80 MPa.
12. A method of preparing a thermoplastic resin composition comprising:
desalting a waste polyester fishing net having an Intrinsic Viscosity (IV) of 0.6dl/g to 0.9dl/g to obtain waste fishing net pellets and subjecting the waste fishing net pellets to sheet molding to manufacture a recovered molded article comprising a total of 60 to 99.9 wt% of Ca, fe and S and a total of 0.1 to 40 wt% of Na, mg, al, si, K, ti, ni, zn, sb and Cl based on a total of 100 wt% of an inorganic component measured using ICP-OES equipment; and
Melt kneading and extruding the recovered molded article, a polyester resin having an Intrinsic Viscosity (IV) of less than 1.0dl/g, a reinforcing resin and a filler fiber,
wherein 37.ltoreq.a.ltoreq.59.2, 15.ltoreq.b.ltoreq.19.9, 20.ltoreq.c.ltoreq.34.9, and 5.ltoreq.d.ltoreq.14.9 are satisfied simultaneously when the weight of the polyester resin is a, the weight of the reinforcing resin is b, the weight of the filler fiber is c, and the weight of the recovered molded article is d.
13. A molded article produced using the thermoplastic resin composition according to any one of claims 1 to 11.
14. The molded article of claim 13, wherein the molded article is an automotive part.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2022-0011939 | 2022-01-27 | ||
| KR1020220184385A KR20230115882A (en) | 2022-01-27 | 2022-12-26 | Thermoplastic resin composition and molded product |
| KR10-2022-0184385 | 2022-12-26 | ||
| PCT/KR2022/021635 WO2023146143A1 (en) | 2022-01-27 | 2022-12-29 | Thermoplastic resin composition and molded article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117098808A true CN117098808A (en) | 2023-11-21 |
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|---|---|---|---|
| CN202280021454.XA Pending CN117098808A (en) | 2022-01-27 | 2022-12-29 | Thermoplastic resin composition and molded article |
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| CN (1) | CN117098808A (en) |
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