CN117083339A - Thermoplastic resin composition and molded article - Google Patents
Thermoplastic resin composition and molded article Download PDFInfo
- Publication number
- CN117083339A CN117083339A CN202380010836.7A CN202380010836A CN117083339A CN 117083339 A CN117083339 A CN 117083339A CN 202380010836 A CN202380010836 A CN 202380010836A CN 117083339 A CN117083339 A CN 117083339A
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- China
- Prior art keywords
- weight
- compound
- resin composition
- thermoplastic resin
- aromatic vinyl
- Prior art date
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- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 117
- 239000011342 resin composition Substances 0.000 title claims abstract description 113
- 229920000728 polyester Polymers 0.000 claims abstract description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 151
- 229920001577 copolymer Polymers 0.000 claims description 116
- -1 polybutylene terephthalate Polymers 0.000 claims description 99
- 229920000642 polymer Polymers 0.000 claims description 78
- 229920005989 resin Polymers 0.000 claims description 74
- 239000011347 resin Substances 0.000 claims description 74
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 57
- 239000002699 waste material Substances 0.000 claims description 49
- 229920000578 graft copolymer Polymers 0.000 claims description 43
- 229920001225 polyester resin Polymers 0.000 claims description 33
- 239000004645 polyester resin Substances 0.000 claims description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 23
- 239000000654 additive Substances 0.000 claims description 23
- 238000005259 measurement Methods 0.000 claims description 22
- 239000008188 pellet Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 230000000996 additive effect Effects 0.000 claims description 17
- 229920003244 diene elastomer Polymers 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 238000011033 desalting Methods 0.000 claims description 16
- 239000004952 Polyamide Substances 0.000 claims description 14
- 229920002647 polyamide Polymers 0.000 claims description 14
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 12
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 9
- 229910045601 alloy Inorganic materials 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
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 239000002667 nucleating agent Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 239000003063 flame retardant Substances 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- 239000000314 lubricant Substances 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 10
- 230000000694 effects Effects 0.000 abstract description 5
- 150000001993 dienes Chemical class 0.000 description 24
- 239000000178 monomer Substances 0.000 description 21
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 125000005396 acrylic acid ester group Chemical group 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000000523 sample Substances 0.000 description 15
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- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 230000000379 polymerizing effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- 238000012662 bulk polymerization Methods 0.000 description 7
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- 239000003999 initiator Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 230000003014 reinforcing effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000000465 moulding 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
- 239000003643 water by type Substances 0.000 description 6
- 230000002411 adverse Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 235000012438 extruded product Nutrition 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
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- 239000012184 mineral wax Substances 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 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
- 239000000463 material Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 4
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 3
- RLFXJQPKMZNLMP-UHFFFAOYSA-N 2-phenylprop-2-enenitrile Chemical compound N#CC(=C)C1=CC=CC=C1 RLFXJQPKMZNLMP-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 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
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 3
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002296 dynamic light scattering Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-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
- 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
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- 229920000459 Nitrile rubber Polymers 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-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
- 238000013019 agitation Methods 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
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000005520 cutting process 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
- 210000003195 fascia Anatomy 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 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
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 239000004576 sand 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
- 239000002904 solvent Substances 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
- 238000005809 transesterification reaction Methods 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
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- 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
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-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
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-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
- 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
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- GQEFPXSNRRKUHO-UHFFFAOYSA-N 4-methylpent-1-enylbenzene Chemical compound CC(C)CC=CC1=CC=CC=C1 GQEFPXSNRRKUHO-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 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
- 239000004908 Emulsion polymer Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
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- 241000269851 Sarda sarda Species 0.000 description 1
- 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
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 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
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 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
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 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
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 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
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000002550 fecal effect Effects 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
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000005484 gravity Effects 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
- 238000001746 injection moulding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 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
- 150000003254 radicals Chemical group 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 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
- 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
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003440 styrenes Chemical group 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 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 and flexural modulus 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, bending strength 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.10-2022-0017482 filed on 10 month 2 in 2022 by the korean intellectual property office and korean patent application No.10-2022-0188095 filed on 29 month 12 in 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 particularly, the present application relates to a thermoplastic resin composition having tensile strength and flexural modulus equal to or superior to those of a conventional composite material composed of a polyester resin and a reinforcing resin, and a molded article manufactured using the same; has greatly improved impact strength, bending strength and heat distortion temperature under high load; and thus is suitable for lightweight automobile parts requiring high rigidity.
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 and coating properties as a material for automobile parts.
Examples of the reinforcing resin include acrylate-styrene-acrylonitrile graft copolymers and styrene-acrylonitrile copolymers, which have excellent mechanical strength, moldability and long-term properties, and also include monomer-styrene-acrylonitrile copolymers having heat resistance.
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, high coating performance and weight saving are achieved, an environmentally friendly composite material capable of preventing environmental pollution can be provided.
[ related art literature ]
[ patent literature ]
KR 2012-0065330A
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 and flexural modulus equal to or superior to those of conventional polyester composites, and a molded article manufactured using the same; has greatly improved impact strength, bending strength and heat distortion temperature under high load; and thus is suitable for lightweight automobile parts requiring high heat resistance and high rigidity.
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:
12.7 to 20 weight percent of a polyester resin; 1 to 12 wt% of a recycled resin or a polyamide/polyalkylene terephthalate alloy resin; more than 15% by weight and 18% by weight or less of a conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer; more than 15% by weight and 22% by weight or less of a conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer; 27 to 45% by weight of a copolymer composed of an acrylic compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound; and 8 to 12.5 wt% of a maleimide-based polymer.
The recycled resin may be a resin obtained by processing waste fishing nets.
The resin 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 resin obtained by processing the waste fishing net may be desalted recovered resin subjected to desalting.
The polyester resin may be polybutylene terephthalate having an Intrinsic Viscosity (IV) of 1.0 dl/g or more.
The conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer may be an emulsion graft copolymer comprising 40 to 80% by weight of a conjugated diene rubber having an average particle diameter of 100 to 500nm, 10 to 40% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyanide compound.
The conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer may be a bulk polymer comprising 5 to 20% by weight of a conjugated diene rubber having an average particle diameter of 800 to 10,000nm, 50 to 85% by weight of an aromatic vinyl compound, and 10 to 30% by weight of a vinyl cyanide compound.
The conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer and the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer may be represented by 1: a weight ratio (graft copolymer: bulk copolymer) of 0.8 to 1.7 is contained.
The copolymer composed of the acrylic acid ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound may be a copolymer comprising 40 to 60% by weight of the acrylic acid ester compound, 30 to 40% by weight of the alkyl-substituted aromatic vinyl compound, and 1 to 20% by weight of the vinyl cyanide compound.
The alkyl-substituted aromatic vinyl compound may be styrene substituted with an alkyl group having 1 to 3 carbon atoms.
The maleimide-based polymer may contain 20% by weight or more of a maleimide-based monomer.
The maleimide-based polymer may contain 45 to 55% by weight of a maleimide-based compound, 40 to 50% by weight of an aromatic vinyl compound, and 1 to 10% by weight of maleic acid or an anhydride thereof.
The maleimide compound may be maleimide and/or N- (substituted) maleimide.
The additive may comprise one or more 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 weight of 9.3kJ/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 86 ℃ 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 prepare a recovered resin containing, based on total 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, as measured using ICP-OES equipment; and
melt kneading and extruding 1 to 12% by weight of the recycled resin, 12.7 to 20% by weight of the polyester resin, more than 15% by weight and 18% by weight or less of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, more than 15% by weight and 22% by weight or less of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, 27 to 45% by weight of the copolymer composed of an acrylic acid ester compound-alkyl substituted aromatic vinyl compound-vinyl cyanide compound, 8 to 12.5% by weight of the maleimide-based polymer, and 0.1 to 5% by weight of the additive,
Wherein the thermoplastic resin composition has a heat distortion temperature of 86 ℃ or more, as measured according to standard measurement ISO 75 at 1.80 MPa.
The recycled resin 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, cutting the precut and washed waste fishing net, and extruding the cut waste fishing net.
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 center fascia or door trim.
Advantageous effects
According to the present invention, the present invention has an effect of providing a thermoplastic resin composition having tensile strength and flexural modulus equal to or superior to those of conventional polyester composite materials, and a molded article manufactured using the same; has greatly improved impact strength, bending strength 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 and the molded article according to the present invention can be used for manufacturing automobile parts. In particular, the thermoplastic resin composition and molded article according to the present invention can be used for manufacturing light-weight automobile parts such as center fascia or door trim that require high heat resistance and high rigidity.
Drawings
Fig. 1 is a flowchart showing a process of processing a waste fishing net to prepare a waste fishing net resin, 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 resin 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, unless otherwise defined, a polymer containing a specific compound refers to 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 maleimide-based polymer, and a recycled resin obtained by desalting a waste fishing net are contained, a thermoplastic resin composition having tensile strength and flexural modulus equal to or superior to those of conventional polyester composite materials is prepared; has greatly improved impact strength, bending strength 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 12.7 to 20% by weight of a polyester resin, 1 to 12% by weight of a recycled resin or a polyamide/polyalkylene terephthalate alloy resin, more than 15% by weight and 18% by weight or less of a conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, more than 15% by weight and 22% by weight or less of a conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, 27 to 45% by weight of a copolymer composed of an acrylic compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, and 8 to 12.5% by weight of a maleimide-based polymer. In this case, the present invention has an effect of providing a thermoplastic resin composition having a tensile strength and a flexural modulus equal to or superior to those of conventional polyester composites; has greatly improved impact strength, bending strength and heat distortion temperature under high load; and thus is suitable for lightweight automobile parts requiring high rigidity.
Unless otherwise indicated, the respective contents of the polyester resin, the recycled resin, the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, the copolymer composed of an acrylic acid ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, and the maleimide-based polymer constituting the thermoplastic resin composition of the present invention are based on 100% by weight in total of the components constituting the thermoplastic resin composition: polyester resin, recycled resin, conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, copolymer composed of acrylic ester compound-alkyl substituted aromatic vinyl compound-vinyl cyanide compound, maleimide polymer and additive.
Further, the thermoplastic resin composition of the present invention comprises 12.7 to 20% by weight of a polyester resin, 1 to 12% by weight of a recycled resin or a polyamide/polyalkylene terephthalate alloy resin, more than 15% by weight and 18% by weight or less of a conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, more than 15% by weight and 22% by weight or less of a conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, 27 to 45% by weight of a copolymer composed of an acrylic ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, 8 to 12.5% by weight of a maleimide-based polymer, and 0.1 to 5% by weight of an additive. In this case, the recycled resin is a product obtained by desalting and sheet-forming waste fishing net pellets 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 measured using ICP-OES equipment. In this case, the present invention can provide a thermoplastic resin composition having a tensile strength and a flexural modulus equal to or superior to those of conventional polyester composites; has greatly improved impact strength, bending strength and heat distortion temperature under high load; and thus is suitable for lightweight automobile parts requiring high rigidity.
Hereinafter, each component constituting the thermoplastic resin composition of the present invention is 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.
Polybutylene terephthalate as the polyester resin has an Intrinsic Viscosity (IV) of preferably 1.1dl/g or more, more preferably 1.1dl/g to 1.3dl/g, measured according to ASTM D2857. 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 processability 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, the intrinsic viscosity was measured at 20℃using an Ubbelohde viscometer.
In one embodiment of the present invention, the thermoplastic resin composition is based on the components constituting the thermoplastic resin composition: the polyester resin, the recovery resin, the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, the copolymer composed of an acrylic acid ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, the maleimide-based polymer, and the total weight of the additives may be contained in an amount of 12.7 to 20% by weight, preferably 13 to 19% by weight, more preferably 14 to 18.5% by weight. When the polyester resin is contained in an amount satisfying the above range, a thermoplastic resin composition having an excellent balance between chemical resistance and mechanical properties can be obtained.
Recovery resin
In one embodiment of the present invention, the recycled resin may comprise resin obtained by processing waste fishing nets.
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.
The polyamide may be contained in an amount of 3 to 48 mole%, preferably 5 to 20 mole%, based on the polyethylene terephthalate. When the polyamide is contained in an amount satisfying the above 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 recycled resin may be black chips obtained by desalting waste fishing nets having a size of 2km×80 m according to a process flow chart of fig. 1 described later. At this time, the size corresponds to an approximate size of a fishing net used in a tuna seine boat.
Fig. 1 below is a flowchart showing a process of preparing a recycled resin or a polyamide/polyalkylene terephthalate alloy resin used in examples described later.
According to FIG. 1 below, in step S1, a scrap fishing net (polyamide: 80 wt%, polyethylene terephthalate: 20 wt%) having a size of 2km×80 m is precut using a cutter. The cutting size at the time of precutting is not particularly limited. Further, when about 200kg of waste fishing net is used after cleaning, 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.
Inorganic materials contained in the obtained recovered resin were analyzed using an ICP-OES apparatus, and the results are shown in table 1 below.
TABLE 1
As shown in table 1, the resin 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, A1, si, K, ti, ni, zn, sb and C1 in total of 0.1 to 40 wt%, preferably 10 to 40 wt%, more preferably 20 to 40 wt%, based on 100 wt% of the total inorganic components measured using the ICP-OES apparatus. Within the above range, a thermoplastic resin composition having an excellent balance between mechanical properties and moldability can be obtained.
Based on the components constituting the thermoplastic resin composition: the total weight of the polyester resin, the recycled resin, the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, the copolymer composed of the acrylic acid ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, the maleimide-based polymer, and the additive, the resin obtained by processing the waste fishing net may be contained in an amount of 1 to 12% by weight, preferably 3 to 11% by weight, more preferably 5 to 10% by weight. When the waste fishing net chips are contained in an amount within this range, a thermoplastic resin composition having an excellent balance among chemical resistance, mechanical properties and heat resistance can be obtained.
Conjugated diene-aromatic vinyl compound-vinyl cyanide compound copolymer
The thermoplastic resin composition of the present invention may contain a conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer obtained by graft polymerizing a conjugated diene rubber, an aromatic vinyl compound and a vinyl cyanide compound, and a conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer containing a conjugated diene polymer, an aromatic vinyl compound and a vinyl cyanide compound.
In the thermoplastic resin composition, the weight ratio of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer to the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer (graft copolymer: bulk copolymer) may be 1:0.8 to 1.7, 1:0.8 to 1.5, or 1:0.9 to 1.2. In this case, the thermoplastic resin composition may have tensile strength, elongation and bending strength equal to or superior to those of conventional polyester composite materials, may have greatly improved impact strength, bending modulus and heat distortion temperature under high load, and thus may be used as a material suitable for manufacturing light-weight automobile parts having high rigidity.
Each copolymer is described in detail below.
Conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer
In one embodiment of the present invention, the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer can be obtained by graft polymerizing a conjugated diene rubber, an aromatic vinyl compound and a vinyl cyanide compound. The graft copolymer may impart excellent processability to the thermoplastic resin composition and may act as an impact modifier in molded articles comprising the thermoplastic resin composition.
The conjugated diene rubber may include a modified conjugated diene polymer obtained by graft-polymerizing an aromatic vinyl compound and a vinyl cyanide compound to a conjugated diene polymer prepared by polymerizing a conjugated diene monomer. Here, the conjugated diene polymer may be referred to as a conjugated diene rubber.
For example, the conjugated diene rubber may be a latex (herein, weight is based on solids) obtained by dispersing a colloidal conjugated diene rubber in water. In this case, mechanical strength and processability may be excellent.
The conjugated diene rubber refers to a (co) polymer prepared by polymerizing a conjugated diene compound having a structure in which double bonds and single bonds are alternately arranged. For example, the conjugated diene rubber may be selected from butadiene polymers, butadiene-styrene copolymers, and butadiene-acrylonitrile copolymers.
Further, for example, the conjugated diene monomer may contain one or more selected from 1, 3-butadiene, isoprene, chloroprene and piperylene, preferably 1, 3-butadiene.
For example, the conjugated diene polymer may have an average particle diameter of 0.01 μm to 1 μm, preferably 0.03 μm to 0.8 μm, more preferably 0.05 μm to 0.5 μm. Within this range, the impact strength, processability, surface properties and surface gloss of molded articles produced using the thermoplastic resin composition of the present invention can be further improved.
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 conjugated diene polymer may be contained in an amount of 40 to 80% by weight, preferably 45 to 75% by weight, more preferably 50 to 70% by weight, based on 100% by weight in total of all components constituting the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer. Within this range, the impact strength, processability, surface properties and surface gloss of molded articles produced using the thermoplastic resin composition of the present invention can be further improved.
For example, the shell of the copolymer may have a weight average molecular weight of 70,000g/mol to 300,000g/mol, preferably 80,000g/mol to 170,000g/mol, more preferably 90,000g/mol to 150,000 g/mol. Within this range, mechanical properties can be improved.
The shell of the copolymer may be formed by graft polymerizing an aromatic vinyl compound and a vinyl cyanide compound onto a conjugated diene polymer.
For example, the aromatic vinyl compound may contain one or more selected from styrene, α -methylstyrene, β -methylstyrene, α -ethylstyrene, β -ethylstyrene, vinyltoluene and derivatives thereof, preferably styrene.
For example, the aromatic vinyl compound may be contained in an amount of 10 to 45 wt%, preferably 20 to 40 wt%, more preferably 20 to 30 wt%, most preferably 25 to 30 wt%, based on 100 wt% total of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer. Within this range, the mechanical properties of molded articles produced using the thermoplastic resin composition of the present invention can be further improved.
For example, the vinyl cyanide compound may contain one or more selected from acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α -chloroacrylonitrile, and derivatives thereof, preferably acrylonitrile.
For example, the vinyl cyanide compound may be contained in an amount of 1 to 25 wt%, preferably 5 to 19 wt%, more preferably 7 to 15 wt%, based on 100 wt% total of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer. Within this range, the mechanical properties of molded articles produced using the thermoplastic resin composition of the present invention can be further improved.
The copolymer may be prepared by polymerizing an aromatic vinyl compound with a vinyl cyanide compound in the presence of a conjugated diene polymer using one or more methods selected from emulsion polymerization, suspension polymerization, and bulk polymerization, preferably emulsion polymerization.
The emulsion polymerization may be a graft emulsion polymerization, and may be carried out, for example, at 50 ℃ to 90 ℃, preferably 60 ℃ to 85 ℃.
The emulsion polymerization may be carried out in the presence of an initiator and an emulsifier.
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 total of monomers constituting the copolymer (including the conjugated diene polymer). Within this range, emulsion polymerization can be promoted, and the remaining amount of the initiator in the copolymer can be minimized to an amount of several tens ppm.
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 total of monomers constituting the copolymer (including the conjugated diene polymer). Within this range, emulsion polymerization can be promoted, and the remaining amount of the emulsifier in the 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 modifier 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 total of monomers constituting the copolymer (including the conjugated diene polymer).
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 continuously fed into the reactor after the emulsion polymerization starts, or the emulsion polymerization may be performed while continuously feeding the monomers for a certain period of time.
The resulting conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer may be in the form of a latex, and may be recovered in the form of a dry powder through aggregation, dehydration and drying processes.
As the coagulant for aggregation, it is possible to use: 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 conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer may be contained in an amount of more than 15% by weight and 18% by weight or less, preferably 16% by weight to 18% by weight, more preferably 16% by weight to 18% by weight, based on 100% by weight in total of all components constituting the thermoplastic resin composition (polyester resin, recycled resin, conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, copolymer composed of an acrylic acid ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, maleimide-based polymer, and additive). Within this range, the molded article produced by injecting the thermoplastic resin composition of the present invention can have excellent mechanical properties and injection quality.
Conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer
Since the conjugated diene-aromatic vinyl compound-vinyl cyanide compound copolymer used herein is prepared by bulk polymerization, 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, when bulk polymerization is performed, an organic solvent as a reaction medium, and, if necessary, additives such as a molecular weight regulator and a polymerization initiator are added to the monomer mixture.
As a specific example, the bulk polymerization may be performed by mixing 100 parts by weight of a monomer mixture comprising a conjugated diene polymer, 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, and polymerizing the mixture 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 of preparing the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer may be performed using a continuous processing machine composed of a raw material input pump, a continuous agitation tank into which the reaction raw material is continuously fed, a preheating tank for preheating the polymer solution discharged from the continuous agitation tank, a volatilization tank for volatilizing unreacted monomers and/or reaction medium, a polymer transfer pump, and an extruder for preparing the polymer in pellet form.
At this time, the extrusion process may be performed at 210 to 240 ℃, but the present invention is not limited thereto.
As the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, a commercially available product may be used as long as the product satisfies the definition of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer of the present invention.
In one embodiment of the present invention, for example, the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer may be a copolymer comprising a conjugated diene polymer 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.
The conjugated diene polymer may include a modified conjugated diene polymer obtained by graft-polymerizing an aromatic vinyl compound and a vinyl cyanide compound to a conjugated diene polymer prepared by polymerizing a conjugated diene monomer. Here, the conjugated diene polymer may be referred to as a conjugated diene rubber.
For example, the conjugated diene rubber may be a latex (herein, weight is based on solids) obtained by dispersing a colloidal conjugated diene rubber in water. In this case, mechanical strength and processability may be excellent.
The conjugated diene rubber refers to a (co) polymer prepared by polymerizing a conjugated diene compound having a structure in which double bonds and single bonds are alternately arranged. For example, the conjugated diene rubber may be selected from butadiene polymers, butadiene-styrene copolymers, and butadiene-acrylonitrile copolymers.
Further, for example, the conjugated diene monomer may contain one or more selected from 1, 3-butadiene, isoprene, chloroprene and piperylene, preferably 1, 3-butadiene.
For example, the conjugated diene polymer may have an average particle diameter of 0.01 μm to 1 μm, preferably 0.03 μm to 0.8 μm, more preferably 0.05 μm to 0.5 μm. Within this range, the impact strength, processability, surface properties and surface gloss of molded articles produced using the thermoplastic resin composition of the present invention can be further improved.
For example, the conjugated diene polymer may be contained in an amount of 40 to 80 wt%, preferably 45 to 75 wt%, more preferably 50 to 70 wt%, based on 100 wt% total of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer. Within this range, the impact strength, processability, surface properties and surface gloss of molded articles produced using the thermoplastic resin composition of the present invention can be further improved.
For example, the shell of the copolymer may have a weight average molecular weight of 70,000 g/mol to 300,000 g/mol, preferably 80,000 g/mol to 170,000 g/mol, more preferably 90,000 g/mol to 150,000 g/mol. Within this range, mechanical properties can be improved.
The shell of the copolymer may be formed by graft polymerizing an aromatic vinyl compound and a vinyl cyanide compound onto a conjugated diene polymer.
For example, the aromatic vinyl compound may contain one or more selected from styrene, α -methylstyrene, β -methylstyrene, α -ethylstyrene, β -ethylstyrene, vinyltoluene and derivatives thereof, preferably styrene.
For example, the aromatic vinyl compound may be contained in an amount of 10 to 45 wt%, preferably 20 to 40 wt%, more preferably 20 to 30 wt%, most preferably 25 to 30 wt%, based on 100 wt% total of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer. Within this range, the mechanical properties of molded articles produced using the thermoplastic resin composition of the present invention can be further improved.
For example, the vinyl cyanide compound may contain one or more selected from acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α -chloroacrylonitrile, and derivatives thereof, preferably acrylonitrile.
For example, the vinyl cyanide compound may be contained in an amount of 1 to 25 wt%, preferably 5 to 19 wt%, more preferably 7 to 15 wt%, based on 100 wt% total of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer. Within this range, the mechanical properties of molded articles produced using the thermoplastic resin composition of the present invention can be further improved.
As the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, a commercially available product may be used as long as the product satisfies the definition of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer of the present invention.
For example, the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk 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.
The conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer may be contained in an amount of more than 15% by weight and 22% by weight or less, preferably 16% by weight to 22% by weight, more preferably 16% by weight to 20% by weight, based on the total weight of all components constituting the thermoplastic resin composition (polyester resin, recovery resin, conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, copolymer composed of acrylic acid ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, maleimide-based polymer, and additive). When the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer is contained in an amount satisfying the above range, a thermoplastic resin composition having an excellent balance between chemical resistance and mechanical properties can be obtained.
Consisting of acrylate-alkyl-substituted aromatic vinyl-vinyl cyanide compounds
Copolymer
In one embodiment of the present invention, the copolymer composed of the acrylic acid ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound can be obtained by graft polymerizing an acrylic acid ester compound, an alkyl-substituted aromatic vinyl compound and a vinyl cyanide compound. 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 compound may be contained in an amount of 40 to 47 wt%, preferably 40 to 45 wt%, more preferably 40 to 43 wt%, based on the total weight of all components constituting the copolymer composed of the acrylic compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound. Within this range, weather resistance, impact strength, and scratch resistance may be excellent.
For example, the acrylic compound may be a (meth) acrylic monomer.
In the present disclosure, the (meth) acrylic monomer includes both acrylic monomers and methacrylic monomers.
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 containing an alkyl group having 4 to 8 carbon atoms, more preferably butyl acrylate or ethylhexyl acrylate.
The alkyl-substituted aromatic vinyl compound included in the copolymer composed of the acrylic compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound may include one or more selected from the group consisting of α -methylstyrene, α -ethylstyrene, and p-methylstyrene, with styrene being preferred.
For example, the aromatic vinyl compound contained in the copolymer composed of the acrylic compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound may be contained in an amount of 30 to 37% by weight, preferably 33 to 37% by weight, based on the total weight of all components constituting the copolymer composed of the acrylic compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound. Within this range, mechanical properties such as tensile strength and impact strength, and processability may be excellent.
For example, the alkyl-substituted aromatic vinyl compound may include one or more selected from the group consisting of α -methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, vinyltoluene, vinylxylene, 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 copolymer composed of the acrylic acid ester-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound may include one or more selected from acrylonitrile, methacrylonitrile, phenylacrylonitrile, α -chloroacrylonitrile, and acetonitrile, with acrylonitrile being preferred.
For example, the vinyl cyanide compound contained in the copolymer composed of the acrylic compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound may be contained 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 all components constituting the copolymer composed of the acrylic compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound. 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.
As the copolymer composed of the acrylic acid ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, a commercially available product may be used as long as the product satisfies the definition of the copolymer composed of the acrylic acid ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound of the present invention.
For example, the copolymer composed of the acrylic acid ester-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound may have a weight average molecular weight of 40,000 g/mol to 200,000 g/mol, preferably 60,000 g/mol to 190,000 g/mol, more preferably 80,000 g/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.
The copolymer composed of the acrylic compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound may be contained in an amount of 27 to 45% by weight, preferably 28 to 40% by weight, more preferably 29 to 35% by weight, based on the total weight of all components constituting the thermoplastic resin composition (polyester resin, recovery resin, conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, copolymer composed of the acrylic compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, maleimide-based polymer, and additive). When the copolymer composed of the acrylic compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound is contained in an amount satisfying the above range, a thermoplastic resin composition having an excellent balance among chemical resistance, mechanical properties and heat resistance can be obtained.
Maleimide fecal polymers
In one embodiment of the present invention, the maleimide-based polymer can improve the balance of physical properties of the thermoplastic resin composition. That is, maleimide-based polymers can serve as matrix resins to control surface impact, mechanical properties, processability, coating appearance, and prevent cracking after coating.
For example, the maleimide-based polymer may contain 20 wt% or more, preferably 20 wt% to 80 wt%, more preferably 30 wt% to 60 wt%, still more preferably 40 wt% to 60 wt%, still more preferably 45 wt% to 55 wt% of the maleimide-based monomer, based on the total weight of all components constituting the maleimide-based polymer. Within this range, mechanical properties and heat resistance may be excellent.
The maleimide-based polymer may preferably be a copolymer comprising an N- (substituted) maleimide and an aromatic vinyl compound, more preferably an N- (substituted) maleimide; an unsaturated dicarboxylic acid or anhydride thereof; and aromatic vinyl compounds. Within this range, mechanical properties and heat resistance may be excellent.
When the maleimide-based polymer is produced, the maleimide-based compound, the aromatic vinyl compound and the maleic acid or an anhydride thereof may be fed batchwise or continuously, and the polymerization may be carried out using one or more methods selected from emulsion polymerization, suspension polymerization and bulk polymerization.
Specifically, the maleimide-based polymer may contain 45 to 55% by weight of a maleimide-based compound, 40 to 50% by weight of an aromatic vinyl compound, and 1 to 10% by weight of maleic acid or an anhydride thereof. Within this range, mechanical properties and heat resistance may be excellent.
The maleimide-based compound is preferably maleimide and/or N- (substituted) maleimide, more preferably N- (substituted) maleimide, and as a specific example, may contain one or more selected from the group consisting of N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide. Within this range, mechanical properties and heat resistance may be excellent.
For example, the maleimide-based compound may be contained in an amount of 26 to 34 wt%, preferably 26 to 32 wt%, more preferably 26 to 30 wt%, based on 100 wt% in total of all components constituting the maleimide-based compound. Within this range, the heat resistance, injection moldability and surface gloss at high temperature of the molded article produced using the thermoplastic resin composition of the present invention can be further improved.
The type of aromatic vinyl compound is as described in the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer.
For example, the maleimide-based polymer may contain an aromatic vinyl compound in an amount of 66 to 76 wt%, preferably 68 to 74 wt%, more preferably 70 to 74 wt%, based on 100 wt% of all components constituting the maleimide-based polymer in total. Within this range, the mechanical properties and heat resistance of molded articles produced using the thermoplastic resin composition of the present invention may be excellent.
For example, the maleic acid or anhydride thereof may be contained in an amount of 1 to 10% by weight, preferably 1 to 8% by weight, more preferably 2 to 8% by weight, based on 100% by weight in total of all components constituting the maleimide-based polymer. Within this range, the heat resistance, injection moldability and surface gloss of the molded article containing the above maleimide-based polymer at high temperature can be further improved.
For example, the maleimide-based polymer 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 of the matrix resin can be improved. That is, the balance between mechanical properties, processability and coating appearance can be easily controlled.
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.
As the maleimide-based polymer, a commercially available product may be used as long as the product satisfies the definition of the maleimide-based polymer of the present invention.
The maleimide-based polymer may be contained in an amount of 8 to 12.5% by weight, preferably 9 to 12% by weight, more preferably 10 to 11% by weight, based on the total weight of all components constituting the thermoplastic resin composition (polyester resin, recovery resin, conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, copolymer composed of acrylic acid ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, maleimide-based polymer, and additive). When the maleimide-based polymer is contained in an amount satisfying the above range, a thermoplastic resin composition having an excellent balance among chemical resistance, mechanical properties and heat resistance can be obtained.
Thermoplastic resin composition
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 the mineral wax 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 inorganic 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 plug gold_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 commercially available 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, preferably 0.05 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, based on the total weight of all components constituting the thermoplastic resin composition (polyester resin, recycled resin, conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, copolymer composed of acrylic acid ester compound-alkyl substituted aromatic vinyl compound-vinyl cyanide compound, maleimide-based polymer, and additive). Within this range, excellent releasability and injectability can be achieved.
In addition, processing aids, pigments, colorants, and the like may be included as necessary.
As a specific example, when the thermoplastic resin composition comprises the above-mentioned 12.7 to 20% by weight of a polyester resin, 1 to 12% by weight of a recycled resin or a polyamide/polyalkylene terephthalate alloy resin, more than 15 and 18% by weight of a conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, more than 15 and 22% by weight of a conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, 27 to 45% by weight of a copolymer composed of an acrylic acid ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, 8 to 12.5% by weight of a maleimide polymer and 0.1 to 5% by weight of an additive, and the recycled resin is a black chip obtained by desalting a waste fishing net having a size of 2km×80m and is an extruded product obtained by molding a waste net pellet and a sheet, wherein the total of the inorganic net as measured by ICP-S equipment, the thermoplastic resin has a total flexural modulus of from 27 to 45% by weight to 20% by weight, an organic tensile strength which can be improved by a total of 0.60% to 60% by weight of a thermoplastic resin, an organic impact strength, a high tensile strength of which can be more than or more than a conventional thermoplastic resin, a high in total of 0.38.60% by weight and a total of 0.38% by weight of the total, a thermoplastic resin, and a high impact strength of which can be produced.
In one embodiment of the present invention, the thermoplastic resin composition may have a flexural modulus of 2, 100MPa or more, as a specific example, 2, 100MPa to 2, 150MPa, 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 9.3kJ/m, as measured according to Standard measurement ISO 180/1A 2 Above, as a specific example, 9.3kJ/m 2 To 12kJ/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 86 ℃ or more, as a specific example, 88 ℃ to 90 ℃ 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 47MPa or more, as a specific example, 47MPa to 52MPa, 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 a melt flow index (260 ℃,5 kg) of 10.0g/10min or more, as a specific example, 10.0g/10min to 12.0g/10min, as measured according to standard measurement ISO 1133. In this case, the processability may be excellent.
As a specific example, when the thermoplastic resin composition comprises the above-mentioned 12.7 to 20% by weight of the polyester resin, 1 to 12% by weight of the recycled resin or the polyamide/polyalkylene terephthalate alloy resin, more than 15% by weight and 18% by weight or less of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, more than 15% by weight and 22% by weight or less of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, 27 to 45% by weight of the copolymer composed of the acrylic acid ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, 8 to 12.5% by weight of the maleimide-based polymer, and 0.01 to 5% by weight of the additive, and is an extruded product of the thermoplastic resin composition having a temperature of 86 ℃ or more as measured according to the standard measurement ISO 75 at 1.80MPa, the thermoplastic resin composition may have a tensile strength equal to or better than that of the conventional polyester composite, an elongation and a bending strength, may have a greatly improved heat distortion strength at a high impact strength, may be suitable for the manufacture of high-load-carrying parts, and a high heat distortion strength may be suitable for the manufacture of high-load-carrying parts.
In addition, when the thermoplastic resin composition comprises the above-mentioned 12.7 to 20% by weight of a polyester resin, 1 to 12% by weight of a recycled resin or a polyamide/polyalkylene terephthalate alloy resin, more than 15 and 18% by weight of a conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, more than 15 and 22% by weight of a conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, 27 to 45% by weight of a copolymer composed of an acrylic compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, 8 to 12.5% by weight of a maleimide polymer and 0.1 to 5% by weight of an additive, and the recycled resin is a black chip obtained by desalting a waste net having a size of 2km×80m and is an extruded product obtained by molding a waste net pellet and a sheet, wherein the total of the total amount of the components measured using an ICP-S apparatus is 100% by weight based on a total of the inorganic components, the total of which can have a flexural modulus of no more than 0.60% by weight and a high flexural strength, a high flexural strength of a thermoplastic resin can be produced at a total of 0.60% by weight and a high flexural strength, a high impact strength of a total of 0.60% to 60% by weight, a high impact strength and a high suitable for a thermoplastic resin is produced.
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 may be prepared in the form of pellets by a method of melt-extruding a mixture of components and additives using an extruder, and the pellets may be used for manufacturing injection molded articles and extrusion molded articles.
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 230 ℃ to 250 ℃. 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 60 ℃ to 120 ℃, preferably 80 ℃ to 100 ℃. When the mold temperature is lower than 60 ℃, the appearance may deteriorate, and the effect of improving crystallinity and physical properties due to annealing may not be significant. When the mold temperature exceeds 120 ℃, 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 230 ℃ to 260 ℃, 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.
According to an embodiment of the present invention, the method of preparing a thermoplastic resin composition may include: a step 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 molding to prepare a recovered resin, wherein the recovered resin contains, based on a total of 100% by weight of inorganic components, 60% by weight to 99.9% by weight of Ca, fe and S and 0.1% by weight to 40% by weight of Na, mg, A1, si, K, ti, ni, zn, sb and Cl, as measured using an ICP-OES apparatus; and
a step of melt-kneading and extruding 1 to 12% by weight of a recycled resin, 12.7 to 20% by weight of a polyester resin, more than 15% by weight and 18% by weight or less of a conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, more than 15% by weight and 22% by weight or less of a conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, 27 to 45% by weight of a copolymer composed of an acrylic ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, 8 to 12.5% by weight of a maleimide-based polymer, and 0.1 to 5% by weight of an additive.
As a specific example, the method of preparing the thermoplastic resin composition may include: a step 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 molding to prepare a recovered resin, wherein the recovered resin contains, 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, as measured using an ICP-OES apparatus; and a step of melt-kneading and extruding the recovered resin, the polyester resin having an Intrinsic Viscosity (IV) of less than 1.0 dl/g, the reinforcing resin, and the filler fiber.
< 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 and 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 such as a center instrument panel or door trim that requires high rigidity and high load heat resistance.
For example, the molded article may have a value of 9.3kJ/m, as measured according to Standard measurement ISO 180/1A 2 Above, preferably 9.3kJ/m 2 To 12kJ/m 2 Is a room temperature impact strength of (c).
Further, for example, the molded article may have a heat distortion temperature of 86 ℃ or more, preferably 88 ℃ to 90 ℃ as measured according to standard measurement ISO 75 at 1.80 MPa.
Further, for example, the molded article may have a flexural modulus of 2, 100MPa or more, preferably 2, 100MPa to 2, 150MPa, as measured according to standard measurement ISO 178 at a span of 64 and a rate of 2 mm/min.
Accordingly, 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 and parts for office equipment, in addition to automobile parts.
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.
Examples (example)
The components used in the examples and comparative examples of the present invention are as follows.
(A) Polybutylene terephthalate
(A-1) PBT having an intrinsic viscosity of 1.2dl/g
(A-2) PBT having an intrinsic viscosity of 0.8dl/g
(B) Waste fishing net fragments: the black chips of fig. 2C obtained by processing waste fishing net according to the flowchart of fig. 1
(C) Conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer: emulsion polymer (Mw: 78,000 g/mol) comprising 60% by weight of butadiene polymer having an average particle diameter of 300nm, 30% by weight of styrene and 10% by weight of acrylonitrile
(D) Conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer: bulk polymer (Mw: 130,000g/mol to 180,000 g/mol) comprising 60% by weight of butadiene polymer having an average particle diameter of 300nm, 30% by weight of styrene and 10% by weight of acrylonitrile
( E) Copolymers composed of acrylic acid ester-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound (butyl acrylate polymer: 50% by weight, α -methylstyrene: 35 wt.%, acrylonitrile: 15 wt%, mw:100,000g/mol )
( F) A copolymer composed of a styrene-vinyl cyanide compound (styrene: 72% by weight, acrylonitrile: 28 wt%, mw:130,000g/mol )
( G) Maleimide-based polymers (phenylmaleimide: 52 wt.%, maleic anhydride: 2% by weight of styrene: 46 wt%, mw:130,000g/mol )
Antioxidants (phenolic antioxidants): pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate)
-a nucleating agent: polyethylene wax (LDPE wax)
Hydrolysis inhibitor (transesterification inhibitor): from chemical NaH 2 PO 4 The sodium dihydrogen phosphate shown in examples 1 to 4 and comparative examples 1 to 10
Each component was added according to the content described in table 2 below, and melt-kneaded using a twin-screw extruder heated to 230 to 250 ℃ to prepare a resin composition in the form of pellets. For reference, the antioxidant was added in an amount of 0.5 wt%, the nucleating agent was added in an amount of 0.5 wt%, and the hydrolysis inhibitor was added in an amount of 0.35 wt%.
After the obtained pellets were dried at 80 ℃ for more than 4 hours, the dried pellets were injected using a screw type injection machine at a mold temperature of 80 ℃, a hopper temperature of 230 ℃ to 250 ℃ and a nozzle temperature of 230 ℃ to 250 ℃ 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 table 3 below.
* Melt flow index (unit: g/10 min): melt flow index was measured at 260℃under a load of 2.16kg according to ISO 1133.
* Impact Strength (unit: KJ/m) 2 ): impact strength was measured according to ISO 180/1A (notched, room temperature at 23 ℃).
* Tensile strength (unit: MPa) and elongation (unit:%): tensile strength and elongation were measured according to ISO 527 at room temperature at 23℃and a rate of 50 mm/min.
* Flexural Strength (unit: MPa) and flexural modulus (unit: MPa): the 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 (unit:. Degree. C.): the heat distortion temperature is measured according to ISO 75 under a high load of 1.80 MPa.
* Density (unit: g/cm) 3 ): the density was measured according to ISO 1183.
TABLE 2
TABLE 3
As shown in tables 2 and 3, in the case of examples 1 to 4 using polybutylene terephthalate and a recovered resin obtained by desalting a waste fishing net as an essential component, and comprising a conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, a conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, a copolymer composed of an acrylic acid ester-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, and a maleimide-based polymer in a predetermined content ratio, the melt flow index was 16g/10min to 18g/10min, the Izod impact strength was 9.2kJ/m 2 To 12kJ/m 2 The above, the tensile strength is 47MPa to 52MPa, the flexural strength is 161MPa or more, the flexural modulus is 8,000 MPa or more, and the heat distortion temperature is 80 ℃ or more. Based on these results, it can be confirmed that examples 1 to 4 have a good balance of physical properties among high rigidity, high load heat resistance and specific gravity.
On the other hand, in the case of comparative example 1 containing an unsuitable amount of polybutylene terephthalate constituting the matrix resin, the heat distortion temperature and impact strength are lowered.
In addition, in the case of comparative examples 2 and 3 containing an unsuitable amount of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, the tensile strength and heat distortion temperature are reduced.
In addition, in the case of comparative example 4 which does not contain the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, an extruded product could not be produced. In the case of comparative example 5 in which the amount of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer is reduced and the amount of the copolymer composed of the acrylic acid ester-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound is increased as compared with comparative example 4, the impact strength is lowered.
In addition, in the case of comparative example 6 containing no maleimide-based polymer, the tensile strength, flexural strength and heat distortion temperature were lowered.
Further, in the case of comparative examples 7 and 8, which do not contain the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer and contain an excessive amount of maleimide-based polymer, the impact strength, tensile strength, flexural strength and heat distortion temperature are lowered.
Further, in the case of comparative example 9 containing a copolymer composed of a styrene-vinyl cyanide compound instead of the copolymer composed of an acrylic acid ester-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound and a maleimide-based polymer of example 1, the flexural strength, flexural modulus and heat distortion temperature were lowered, and the melt flow index was poor.
Further, in the case of comparative example 10 in which the intrinsic viscosity of polybutylene terephthalate is out of the proper range, the impact strength and the melt flow index are adversely affected, as compared with example 1.
In summary, when the recycled resin, the polyester resin, the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, the copolymer composed of the acrylic acid ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, and the maleimide-based polymer satisfying the specific physical properties described in the present invention are contained in an appropriate composition ratio, high heat resistance and high rigidity can be obtained while satisfying the environmental friendliness, as compared with the thermoplastic resin composition comprising the conventional polyester composite containing the fresh polyethylene terephthalate instead of the recycled resin or the polyamide/polyalkylene terephthalate alloy resin.
Claims (15)
1. A thermoplastic resin composition comprising:
12.7 to 20 weight percent of a polyester resin;
1 to 12 wt% of a recycled resin or a polyamide/polyalkylene terephthalate alloy resin;
more than 15% by weight and 18% by weight or less of a conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer;
more than 15% by weight and 22% by weight or less of a conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer;
27 to 45% by weight of a copolymer composed of an acrylic compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound; and
8 to 12.5% by weight of a maleimide-based polymer.
2. The thermoplastic resin composition of claim 1, wherein said recycled resin is a resin obtained by processing waste fishing nets.
3. The thermoplastic resin composition of claim 2, wherein the resin obtained by processing the waste fishing net comprises Ca, fe and S in a total of 60 to 99.9 wt% and Na, mg, al, si, K, ti, ni, zn, sb and Cl in a total of 0.1 to 40 wt%, based on a total of 100 wt% of inorganic components, measured using ICP-OES equipment.
4. The thermoplastic resin composition according to claim 2, wherein the resin obtained by processing the waste fishing net is a desalted recovered resin subjected to desalting.
5. The thermoplastic resin composition according to claim 1, wherein the polyester resin is polybutylene terephthalate having an Intrinsic Viscosity (IV) of 1.0dl/g or more.
6. The thermoplastic resin composition according to claim 1, wherein the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer is a graft copolymer comprising 40 to 80% by weight of a conjugated diene rubber having an average particle diameter of 100 to 500nm, 10 to 40% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyanide compound.
7. The thermoplastic resin composition according to claim 1, wherein the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer is a copolymer comprising 5 to 20% by weight of a conjugated diene rubber having an average particle diameter of 800nm to 10,000nm, 50 to 85% by weight of an aromatic vinyl compound, and 10 to 30% by weight of a vinyl cyanide compound.
8. The thermoplastic resin composition according to claim 1, wherein the copolymer composed of an acrylic compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound is a copolymer comprising 40 to 60% by weight of an acrylic compound, 30 to 40% by weight of an alkyl-substituted aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyanide compound.
9. The thermoplastic resin composition of claim 1, wherein the maleimide-based polymer comprises 45 to 55% by weight of a maleimide-based compound, 40 to 50% by weight of an aromatic vinyl compound, and 1 to 10% by weight of maleic acid or an anhydride thereof.
10. The thermoplastic resin composition of claim 1, wherein said thermoplastic resin composition comprises 0.1 to 5 weight percent of one or more additives selected from the group consisting of antioxidants, lubricants, hydrolysis inhibitors, flame retardants, nucleating agents, heat stabilizers, light stabilizers, and thickeners.
11. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a weight of 9.3kJ/m as measured according to standard measurement ISO 180/1A 2 The above room temperature impact strength.
12. The thermoplastic resin composition of claim 1, wherein said thermoplastic resin composition has a heat distortion temperature of 86 ℃ or greater as measured according to standard measurement ISO 75 at 1.80 MPa.
13. 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 forming to prepare a recovered resin containing, based on 100% by weight total of inorganic components, 60% by weight to 99.9% by weight of Ca, fe and S and 0.1% by weight to 40% by weight total of Na, mg, al, si, K, ti, ni, zn, sb and Cl, as measured using an ICP-OES apparatus; and
melt kneading and extruding 1 to 12% by weight of the recycled resin, 12.7 to 20% by weight of the polyester resin, more than 15 to 18% by weight of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound graft copolymer, more than 15 to 22% by weight of the conjugated diene-aromatic vinyl compound-vinyl cyanide compound bulk copolymer, 27 to 45% by weight of the copolymer composed of an acrylic ester compound-alkyl-substituted aromatic vinyl compound-vinyl cyanide compound, 8 to 12.5% by weight of the maleimide-based polymer, and 0.1 to 5% by weight of the additive,
Wherein the thermoplastic resin composition has a heat distortion temperature of 86 ℃ or more, as measured according to standard measurement ISO 75 at 1.80 MPa.
14. A molded article produced using the thermoplastic resin composition according to any one of claims 1 to 12.
15. The molded article of claim 14, wherein the molded article is an automotive part.
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|---|---|---|---|
| KR10-2022-0017482 | 2022-02-10 | ||
| KR1020220188095A KR20230120983A (en) | 2022-02-10 | 2022-12-29 | Thermoplastic resin composition and molded product |
| KR10-2022-0188095 | 2022-12-29 | ||
| PCT/KR2023/000004 WO2023153641A1 (en) | 2022-02-10 | 2023-01-02 | Thermoplastic resin composition, and molded product |
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| CN117083339A true CN117083339A (en) | 2023-11-17 |
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