CN118515961B - Gas-assisted formed PC/PET/POK alloy material and preparation method thereof - Google Patents
Gas-assisted formed PC/PET/POK alloy material and preparation method thereof Download PDFInfo
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- CN118515961B CN118515961B CN202410985735.8A CN202410985735A CN118515961B CN 118515961 B CN118515961 B CN 118515961B CN 202410985735 A CN202410985735 A CN 202410985735A CN 118515961 B CN118515961 B CN 118515961B
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- 239000000956 alloy Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 158
- 239000011347 resin Substances 0.000 claims abstract description 158
- 238000000465 moulding Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 34
- 230000003078 antioxidant effect Effects 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 33
- 239000000314 lubricant Substances 0.000 claims description 27
- 239000000155 melt Substances 0.000 claims description 25
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical class CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002608 ionic liquid Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 229920000554 ionomer Polymers 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Chemical class 0.000 claims description 17
- 150000002978 peroxides Chemical class 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 10
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 9
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 9
- -1 1-hexyl-2,3,5-trimethylpyrazole hydrogen sulfate Chemical compound 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 6
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 6
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- TVEOIQKGZSIMNG-UHFFFAOYSA-N hydron;1-methyl-1h-imidazol-1-ium;sulfate Chemical compound OS([O-])(=O)=O.C[NH+]1C=CN=C1 TVEOIQKGZSIMNG-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims 2
- KXCVJPJCRAEILX-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;hydrogen sulfate Chemical compound OS([O-])(=O)=O.CCCCN1C=C[N+](C)=C1 KXCVJPJCRAEILX-UHFFFAOYSA-M 0.000 claims 1
- TVCNKZCRZIIOOR-UHFFFAOYSA-M 1-hexyl-3-methylimidazol-3-ium;hydrogen sulfate Chemical compound OS([O-])(=O)=O.CCCCCC[N+]=1C=CN(C)C=1 TVCNKZCRZIIOOR-UHFFFAOYSA-M 0.000 claims 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 claims 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000000071 blow moulding Methods 0.000 abstract description 2
- 239000004417 polycarbonate Substances 0.000 description 112
- 229920001470 polyketone Polymers 0.000 description 110
- 229920000139 polyethylene terephthalate Polymers 0.000 description 97
- 239000005020 polyethylene terephthalate Substances 0.000 description 97
- 239000002994 raw material Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 19
- 238000002844 melting Methods 0.000 description 16
- 230000008018 melting Effects 0.000 description 16
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 15
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 15
- 238000010008 shearing Methods 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 229920000515 polycarbonate Polymers 0.000 description 14
- 239000004425 Makrolon Substances 0.000 description 13
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 13
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- ZNNXXAURXKYLQY-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCN1CN(C)C=C1 ZNNXXAURXKYLQY-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 125000004185 ester group Chemical group 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000005275 alloying Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012994 photoredox catalyst Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009966 trimming Methods 0.000 description 3
- WEZFRVSBUPJHFG-UHFFFAOYSA-N 3-hexyl-1-methyl-1,2-dihydroimidazol-1-ium;hydrogen sulfate Chemical compound OS([O-])(=O)=O.CCCCCCN1C[NH+](C)C=C1 WEZFRVSBUPJHFG-UHFFFAOYSA-N 0.000 description 2
- 239000004201 L-cysteine Substances 0.000 description 2
- 229920004099 Makrolon® ET3113 Polymers 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- ZXIVNGSTMBBPBL-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxy-2-methylphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1C ZXIVNGSTMBBPBL-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ILWVABLRFKUOOO-UHFFFAOYSA-N [3-[2-(3,5-ditert-butyl-4-hydroxyphenyl)-2-methylpropanoyl]oxy-2,2-bis[[2-(3,5-ditert-butyl-4-hydroxyphenyl)-2-methylpropanoyl]oxymethyl]propyl] 2-(3,5-ditert-butyl-4-hydroxyphenyl)-2-methylpropanoate Chemical compound CC(C(=O)OCC(COC(C(C)(C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)C)=O)(COC(C(C)(C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)C)=O)COC(C(C)(C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)C)=O)(C)C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C ILWVABLRFKUOOO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of polymers, in particular to a gas-assisted formed PC/PET/POK alloy material and a preparation method thereof. The alloy material comprises the following components: PC resin, PET resin, POK resin and compatibilizer; wherein the weight ratio of the PC resin to the PET resin is 1: (0.08-0.35); the weight ratio of the PC resin to the POK resin is 1: (0.08-0.35). The PC/PET/POK alloy material prepared by the method has the advantages of high strength, high impact, excellent weather resistance, heat resistance and chemical resistance and heat release, and is particularly suitable for the manufacturing production of gas-assisted molding and blow molding products.
Description
Technical Field
The invention relates to the technical field of polymers, in particular to a gas-assisted formed PC/PET/POK alloy material and a preparation method thereof.
Background
Polycarbonates (hereinafter abbreviated as PC) are amorphous high molecular polymers having excellent properties such as high impact, excellent weather resistance, V2-class flame retardancy, etc. The method is widely applied to exterior trimming parts of automobiles. The defects are as follows: because PC molecular chains contain benzene rings, the molecular chains are hindered from moving and are not easy to arrange regularly, the PC surface hardness is low, the pencil hardness is less than HB, and the surface of the PC is easy to scratch. PC is very susceptible to high temperature hydrolysis due to the ester groups contained in the molecule.
Polyethylene terephthalate (PET) is a semi-crystalline polymer, has high temperature resistance, creep resistance, fatigue resistance, good weather resistance and the like, has good resistance to weak acid, weak base, salt, organic solvent and other chemical substances, and is not easy to corrode. Disadvantages: low impact strength, containing ester group, and easy hydrolysis.
Polyketone (POK) is a high-crystalline high-molecular polymer, is a novel green polymer material synthesized from carbon monoxide and olefin (ethylene and propylene), and has high wear resistance, hydrolysis resistance, excellent chemical resistance, excellent flowability and molding processability. Disadvantages: the heat resistance and rigidity (flexural modulus: 1800 MPa) were relatively low.
Along with the progress of technology and the functional requirements of special products, such as automobile door outer handles, automobile tail wings and the like, the requirements on materials are more and more strict, the product can realize dimensional stability in the current gas-assisted molding mode except the common injection molding means, but the gas-assisted molding product has very strict requirements on materials, and single polymer resin has different defects and can not realize gas-assisted molding well.
Disclosure of Invention
The invention aims to solve the problem of single PC, PET, POK, and provides a gas-assisted formed PC/PET/POK alloy material and a preparation method thereof, the gas-assisted formed PC/PET/POK alloy material is easy to process, the PC/PET/POK alloy material prepared by the method has the excellent performances of high strength, high impact, excellent weather resistance, heat resistance and chemical resistance, and can be widely used for the production of automobile exterior trimming parts.
In order to achieve the above object, the first aspect of the present invention provides a gas-assist molded PC/PET/POK alloy material, comprising the following components: PC resin, PET resin, POK resin and compatibilizer; wherein the weight ratio of the PC resin to the PET resin is 1: (0.08-0.35); the weight ratio of the PC resin to the POK resin is 1: (0.08-0.35); the preparation method of the compatilizer comprises the following steps: and (3) carrying out melt extrusion granulation on 80-98 parts by mass of POK resin, 2-20 parts by mass of Glycidyl Methacrylate (GMA), 0.05-0.1 part by mass of peroxide initiator and 0-10 parts by mass of ionic liquid to obtain the compatilizer.
Preferably, the weight ratio of the PC resin to the PET resin is 1: (0.10-0.22); the weight ratio of the PC resin to the POK resin is 1: (0.10-0.22); the weight ratio of the PC resin to the compatilizer is 1: (0.01-0.10).
Preferably, the difference between the melt index of the PC resin at 300 ℃/1.2 kg and the melt index of the POK resin at 240 ℃/1.2 kg is 0g/10min to 45g/10min, preferably 0g/10min to 5g/10 min; the melt index of the PC resin at 300 ℃/1.2 kg is 5g/10 min-15 g/10min, preferably 5g/10 min-10 g/10min; the melt index of the POK resin at 240 ℃/1.2 kg is 5g/10 min-60 g/10min, preferably 5g/10 min-10 g/10min; the PET resin has an intrinsic viscosity of 0.8dl/g to 1.2dl/g.
Preferably, the preparation method of the compatilizer comprises the following steps: and (3) carrying out melt extrusion granulation on 90-98 parts by mass of POK resin, 2-8 parts by mass of Glycidyl Methacrylate (GMA), 0.1-0.5 part by mass of peroxide initiator and 5-7 parts by mass of ionic liquid to obtain the compatilizer.
Preferably, the ionic liquid is selected from at least one of 1-hexyl-3-methylimidazole bisulfate, 1-butyl-3-methylimidazole bisulfate, 1-methylimidazole bisulfate and 1-hexyl-2, 3, 5-trimethylpyrazole bisulfate.
Preferably, the alloy material further comprises an antioxidant; the alloy material is calculated by 100 weight parts, and the proportion of the antioxidant is 0.2 to 2.0 parts; the antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is selected from n-stearyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and/or pentaerythritol tetrakis [ methyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and the auxiliary antioxidant is selected from tris [2, 4-di-tert-butylphenyl ] phosphite and tetrakis (2, 4-di-tert-butylphenyl-4, 4' -biphenyl) bisphosphonate.
Preferably, the alloy material further comprises a lubricant; the alloy material is calculated by 100 weight parts, and the proportion of the lubricant is 0.2 to 2.0 parts; the lubricant includes at least one of pentaerythritol stearate (PETS), N' -ethylene bis-stearamide (EBS), ethylene acrylic acid copolymerized metal salt ionomer, and stearic acid erucamide.
The second aspect of the invention provides a preparation method of a gas-assisted formed PC/PET/POK alloy material, which comprises the following steps: the components of the alloy material are mixed, and the mixed materials are subjected to melt extrusion, drawing and granulation by a double-screw extruder to obtain the PC/PET/POK alloy material.
Preferably, the mixing conditions include: the rotating speed is 80r/min-120r/min, and stirring is carried out for 15min-20min; the screw diameter of the double screw extruder is 40mm, and the length-diameter ratio L/D is 44; the temperature of the twin-screw extruder from a feed inlet to a head outlet is 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃ and die head temperature 230-260 ℃ in sequence; the double screw rotating speed of the double screw extruder is 350r/min-450r/min.
Compared with the prior art, the invention has at least the following beneficial effects:
According to the invention, PC resin, PET resin and POK resin in a specific proportion are introduced to carry out alloying in the presence of a compatilizer, and the provided gas-assisted formed PC/PET/POK alloy material can improve the stress cracking defect of single PC, improve the hydrolysis resistance of PC and PET, and has high strength, high impact, excellent weather resistance, heat resistance and chemical resistance. The modified plastic adopts high-viscosity raw materials for modification processing, can be used for producing automobile exterior trimming parts, and is particularly suitable for manufacturing and producing gas-assisted molding and blow molding products, such as automobile door outer handles, automobile tail wings and the like.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description is presented herein by way of illustration and explanation only and is not intended to represent or limit the scope of the present invention as claimed.
The first aspect of the invention provides a gas-assist formed PC/PET/POK alloy material, which comprises the following components: PC resin, PET resin, POK resin and compatibilizer; wherein the weight ratio of the PC resin to the PET resin is 1: (0.08-0.35); the weight ratio of the PC resin to the POK resin is 1: (0.08-0.35); the preparation method of the compatilizer comprises the following steps: and (3) carrying out melt extrusion granulation on 80-98 parts by mass of POK resin, 2-20 parts by mass of Glycidyl Methacrylate (GMA), 0.05-0.1 part by mass of peroxide initiator and 0-10 parts by mass of ionic liquid to obtain the compatilizer.
According to the invention, by introducing PC resin, PET resin and POK resin in a specific proportion to carry out alloying in the presence of a compatilizer, the alloy material prepared from the alloy material has the advantages of high strength, high impact, excellent weather resistance, heat resistance and chemical resistance on the basis of keeping the respective advantages of the PC resin, the PET resin and the POK resin.
In the present invention, the weight ratio of PC resin to PET resin is 1:0.10, 1:0.11, 1:0.12, 1:0.13, 1:0.15, 1:0.18, 1:0.21, 1:0.22, 1:0.26, 1:0.28, 1: 30. 1:0.33, 1:0.35, other specific ratios not listed in this ratio range are equally applicable, and any two specific ratio composition ranges are equally applicable.
In the present invention, the weight ratio of PC resin to POK resin is 1:0.10, 1:0.11, 1:0.12, 1:0.13, 1:0.15, 1:0.18, 1:0.21, 1:0.22, 1:0.26, 1:0.28, 1: 30. 1:0.33, 1:0.35, other specific ratios not listed in this ratio range are equally applicable, and any two specific ratio composition ranges are equally applicable.
As a preferable mode of the invention, the weight ratio of the PC resin to the PET resin is 1: (0.10-0.22); the weight ratio of the PC resin to the POK resin is 1: (0.10-0.22); the weight ratio of the PC resin to the compatilizer is 1: (0.01-0.10).
In the present invention, the weight ratio of PC resin to compatibilizer is 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, 1:0.10, preferably 1: (0.03-0.08), other specific ratios not enumerated in the present range of ratios, as well as any two specific ratio combinations.
In the invention, the inventor finds that if the dosage of PC resin is too small, the strength of the product is reduced, the dosage of PET resin is too much, the fluidity of the material is too high, the gas-assisted molding is not facilitated, the dosage is too small, and the product is easy to paint and crack; the PC/PET/POK alloy material has the advantages that the PC resin, the PET resin, the POK resin and the compatilizer in specific proportions are controlled to optimize the mechanical comprehensive performance of the PC/PET/POK alloy material, the PET resin, the POK resin and the compatilizer can be used as sea components, the PET resin, the POK resin and the compatilizer are jointly used as island components to form the island components which are dispersed in sea components in a continuous phase, and each component in specific proportions has better synergistic toughening effect on multiple chain segments, so that the strength is ensured, the toughness of the material is greatly improved, and the compatilizer enables the PC resin, the PET resin and the POK resin to have better compatibility, thereby being beneficial to improving the heat resistance, the chemical resistance and other performances of the material.
As a preferred embodiment of the present invention, the difference between the melt index of the PC resin at 300 ℃/1.2 kg and the melt index of the POK resin at 240 ℃/1.2 kg is 0g/10min to 45g/10min, for example, 0 g/10min、0.5 g/10min、0.6 g/10min、0.9 g/10min、1.0 g/10min、1.5 g/10min、3 g/10min、5 g/10min、8 g/10min、10 g/10min、15 g/10min、25 g/10min、30 g/10min、40 g/10min、45 g/10min,, and other specific values not listed in the numerical range are equally applicable, and the range of any two specific values is equally applicable; the melt index of the PC resin is 5g/10min-15g/10min at 300 ℃/1.2 kg, for example, 5g/10min, 6.5 g/10min, 8g/10min, 12g/10min and 15g/10min, other specific values not listed in the numerical range are applicable as well, and the range of any two specific values is applicable as well; the POK resin has a melt index of 5g/10min-60g/10min at 240 ℃/1.2 kg, such as 5g/10min 5.6 g/10min, 6 g/10min, 10 g/10min, 20 g/10min, 30 g/10min, 40 g/10min, 50 g/10min, 60g/10min, other specific values not listed in the numerical range are equally applicable, and the range of any two specific values is equally applicable; the intrinsic viscosity of the PET resin is 0.8dl/g-1.2dl/g,0.8dl/g, 0.9dl/g, 1.0dl/g, 1.2dl/g, and other specific values not enumerated in this numerical range are equally applicable, as are the ranges of any two specific value compositions.
As a preferred embodiment of the present invention, the difference between the melt index of the PC resin at 300 ℃/1.2 kg and the melt index of the POK resin at 240 ℃/1.2 kg is 0.5 g/10min to 5g/10min; as a preferred embodiment of the present invention, the PC resin has a melt index of 5g/10min to 10g/10min at 300 ℃/1.2 kg; the melt index of the POK resin at 240 ℃/1.2 kg is 5g/10 min-10g/10min.
The melt indexes in the invention are all obtained by referring to ISO113 standard test; the intrinsic viscosity is obtained by referring to ASTMD-4603 standard test.
The PC resin, the POK resin and the PET resin can be obtained by market, for example, the brand of the PC resin is Makrolon body ET3113, and the melt index of the PC resin at 300 ℃/1.2 kg is 6.5 g/10min; for example, POK resin has the brand name of CH-610, which is spun by Shanghai, and the intrinsic viscosity of 0.800+/-0.015 dl/g; for example, the POK resin has a melt index of 5.6 g/10min at 240 ℃/1.2 kg, M630A, brand Korean phosphor.
In the invention, the inventor has unexpectedly found that the specific PC resin, PET resin and POK resin can not only balance and increase the mechanical property of the alloy material, but also increase the light transmittance of the alloy material, on one hand, the PC resin can prevent the crystallization of the POK resin and the PET resin or further refine the crystal grains of the POK resin and the PET resin in the alloying process under the action of the specific compatilizer, so that the PC/PET/POK alloy material has better transparency; on the other hand, it is possible that when the difference in melt index between the PC resin and the POK resin is within a specific range, each component in the system has good fluidity and little fluidity between each component during alloying, and finally an alloy material excellent in mechanical properties and high in light transmittance is formed.
As a more preferable technical scheme of the invention, the preparation method of the compatilizer comprises the following steps: and (3) carrying out melt extrusion granulation on 90-98 parts by mass of POK resin, 2-8 parts by mass of Glycidyl Methacrylate (GMA), 0.1-0.5 part by mass of peroxide initiator and 5-7 parts by mass of ionic liquid to obtain the compatilizer.
In the invention, the inventor finds that the POK-g-GMA is used as the material capable of better increasing the comprehensive mechanical property, hydrolysis resistance and light transmittance of the alloy material, probably because the GMA functional group can react with the ester group to end-cap the ester group, the hydrolysis resistance of the material is greatly improved, and the material has a POK main chain, so that when the compatibility of PC, PET and POK is increased, the PC can better block PET and POK crystalline chain segments, the short chain segment of the PC can also block PET and POK crystalline chain segments to a certain extent, and the light transmittance of the material is further increased.
In the present invention, the type of the peroxide initiator is not particularly limited, and may be a peroxide initiator which is conventional in the art, and dicumyl peroxide is exemplified as the advantage of the present invention in the present invention, but the present invention is not limited thereto.
As a more preferable technical scheme of the invention, when preparing the compatilizer, the resin used is the same as PC resin in the alloy material, so that the transparency of the synthetic material is further increased.
As a more preferable embodiment of the present invention, the ionic liquid is at least one selected from the group consisting of 1-hexyl-3-methylimidazole bisulfate, 1-butyl-3-methylimidazole bisulfate, 1-methylimidazole bisulfate and 1-hexyl-2, 3, 5-trimethylpyrazole bisulfate, and preferably 1-butyl-3-methylimidazole bisulfate.
In the invention, the inventor finds through experiments that the compatilizer prepared by adding a specific ionic liquid when preparing the compatilizer can not only increase the light transmittance of the alloy material, but also simultaneously increase the wet heat resistance and the mechanical property of the alloy material, probably because the 1-butyl-3-methylimidazole bisulfate can promote the transesterification in a system and further improve the compatibility of the alloy material, but the inventor finds that the ionic liquid cannot be excessively added, otherwise the melt index of the prepared material is excessively large, which is unfavorable for the processing production of gas-assisted molding
As a more preferable embodiment of the present invention, in the case of the compatibilizing agent, the conditions of melt extrusion include: melt extrusion is carried out by a twin-screw extruder, preferably the twin-screw extruder has a temperature in the following temperature ranges: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 350r/min-450r/min.
In the present invention, the set temperature of each section of the twin-screw extruder temperature is a constant value, but the temperature is generally a range value for the reaction or the equipment itself.
In the invention, auxiliary components can be added into the alloy material according to the requirement.
As a preferable technical scheme of the invention, the alloy material further comprises an antioxidant.
According to the invention, the antioxidant can effectively inhibit the material from being degraded and deteriorated due to heating in the processing and using processes, so that the processing is smooth, and the service life of the plastic part is prolonged.
In the present invention, the antioxidant may be an antioxidant conventional in the art, and the specific kind thereof is not particularly limited, and preferably the antioxidant includes a primary antioxidant selected from n-stearyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate and/or pentaerythritol tetrakis [ methyl- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, and a secondary antioxidant selected from tris [2, 4-di-t-butylphenyl ] phosphite, tetrakis (2, 4-di-t-butylphenyl-4, 4' -biphenyl) bisphosphonate. When the primary antioxidant and the secondary antioxidant are used simultaneously, the proportion of the primary antioxidant and the secondary antioxidant is not particularly limited, and is generally 1:1.
As a preferred technical scheme of the invention, the alloy material further comprises a lubricant; the alloy material is calculated by 100 weight parts, and the proportion of the lubricant is 0.2 to 2.0 parts;
the lubricant includes at least one of pentaerythritol stearate (PETS), N' -ethylene bis-stearamide (EBS), ethylene acrylic acid copolymerized metal salt ionomer, and stearic acid erucamide.
In the present invention, the type of the lubricant is not particularly limited, and a single lubricant may be used alone, or two or more kinds of lubricants may be used simultaneously, for example, the lubricant is N, N' -ethylenebisstearamide and erucamide in a weight ratio of 1:1; for example, the lubricant is pentaerythritol stearate (PETS) to metal salt ionomer in a weight ratio of 1:1.
The specific dispersing agent in the invention can be obtained by the market.
The second aspect of the invention provides a preparation method of a gas-assist formed PC/PET/POK alloy material, which comprises the following steps: the components of the alloy material are mixed, and the mixed materials are subjected to melt extrusion, drawing and granulation by a double-screw extruder to obtain the PC/PET/POK alloy material.
As a preferred embodiment of the present invention, the mixing conditions include: the rotation speed is 80r/min-120r/min, such as 80r/min, 90 r/min, 100 r/min, 110 r/min or 120 r/min; stirring for 15min-20min, for example 15min, 16min, 17min, 18min, 19min, 20min, other specific values not enumerated in the numerical range being equally applicable, as well as any two specific value composition ranges.
In the invention, materials are melted, mixed and sheared in a double-screw extruder through double screws. Extruded by a twin screw extruder. As a preferable technical scheme of the invention, the screw diameter of the double screw extruder is 40mm, and the length-diameter ratio L/D is 44.
As a preferred embodiment of the present invention, the conditions for melt extrusion include: the temperature of the twin-screw extruder from the feed inlet to the outlet of the machine head is 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃ and die head temperature 230-260 ℃ in sequence; the double screw rotating speed of the double screw extruder is 350r/min-450r/min.
The present invention will be described in detail by examples.
The preparation method of POK-g-GMA (homemade) in the following examples is: POK (M630A, korean phosphor, melt index at 240 ℃ C./1.2 kg of 5.6 g/10 min), 94.5 parts by mass, peroxide (DCP) and 5.5 parts by mass of GMA were extruded by a twin screw extruder at the following temperatures: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
In the following examples, PET-g-GMA (homemade) was prepared by: 94.5 parts by mass of PET (CH-610, shanghai, intrinsic viscosity of 0.800+/-0.015 dl/g), 0.3 parts by mass of peroxide (DCP) and 5.5 parts by mass of GMA are extruded by a twin-screw extruder, and the temperatures of all sections of the extruder are as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
In the following examples, the preparation method of POK-g-GMA/ionic liquid A (homemade) comprises the following steps: POK (M630A, korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg of 5.6. 5.6 g/10 min), 94.5 parts by mass, peroxide (DCP) 5.5 parts by mass, GMA5.5 parts by mass and 1-butyl-3-methylimidazole bisulfate 6 parts were reaction-extruded by a twin-screw extruder at the following temperatures: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
In the following examples, the preparation method of POK-g-GMA/ionic liquid B (homemade) comprises the following steps: POK (M630A, korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg of 5.6. 5.6 g/10 min), 94.5 parts by mass, peroxide (DCP) 5.5 parts by mass, GMA5.5 parts by mass and 1-butyl-3-methylimidazole bisulfate 12 parts were reaction-extruded by a twin-screw extruder at the following temperatures: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
Example 1
The embodiment provides a PC/PET/POK alloy material capable of being molded in a gas-assisted mode and a preparation method thereof, wherein the alloy material comprises the following raw materials in parts by weight: the PC resin was Makrolon cube ET3113 (covestro, melt index at 300 ℃ C./1.2 kg of 6.5 g/10 min): 76 parts; PET resin is CH-610 (Shanghai Shangzhan, intrinsic viscosity 0.800+ -0.015 dl/g): 10 parts; the POK resin was M630A (Korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg: 5.6. 5.6 g/10 min): 10 parts; compatibilizing agent POK-g-GMA (homemade): 3 parts; antioxidant 1076 (basf) and antioxidant P-EPQ (basf) (combined in weight ratio 1:1): 0.6 parts; lubricant PETS (niter) and ethylene acrylic acid copolymerized metal salt ionomer a-C540 (ganivill) (in a 1:1 combination by weight): 0.4 parts.
Adding the raw materials with the formula amount into a mixer, mixing for 15min at 100 r/min, then melting, mixing and shearing the uniformly mixed materials through double screws, extruding, drawing and granulating through a machine head to obtain the PC/PET/POK alloy material capable of being molded in a gas-assisted mode. Wherein, the extruder temperature is as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
Example 2
The embodiment provides a PC/PET/POK alloy material capable of being molded in a gas-assisted mode and a preparation method thereof, wherein the alloy material comprises the following raw materials in parts by weight: the PC resin was Makrolon cube ET3113 (covestro, melt index at 300 ℃ C./1.2 kg of 6.5 g/10 min): 73 parts; PET resin is CH-610 (Shanghai Shangzhan, intrinsic viscosity 0.800+ -0.015 dl/g): 8 parts; the POK resin was M630A (Korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg: 5.6. 5.6 g/10 min): 15 parts; compatibilizing agent POK-g-GMA (homemade): 3 parts; antioxidant 1010 (basf) and antioxidant 168 (basf) (in a 1:1 combination by weight): 0.6 parts; lubricant PETS (niter) and ethylene acrylic acid copolymerized metal salt ionomer a-C540 (ganivill) (in a 1:1 combination by weight): 0.4 parts.
Adding the raw materials with the formula amount into a mixer, mixing for 15min at 100 r/min, then melting, mixing and shearing the uniformly mixed materials through double screws, extruding, drawing and granulating through a machine head to obtain the PC/PET/POK alloy material capable of being molded in a gas-assisted mode. Wherein, the extruder temperature is as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
Example 3
The embodiment provides a PC/PET/POK alloy material capable of being molded in a gas-assisted mode and a preparation method thereof, wherein the alloy material comprises the following raw materials in parts by weight: the PC resin was Makrolon cube ET3113 (covestro, melt index at 300 ℃ C./1.2 kg of 6.5 g/10 min): 69 parts; PET resin is CH-610 (Shanghai Shangzhan, intrinsic viscosity 0.800+ -0.015 dl/g): 15 parts; the POK resin was M630A (Korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg: 5.6. 5.6 g/10 min): 10 parts; compatibilizing agent POK-g-GMA (homemade): 5 parts; antioxidant 1010 (basf) and antioxidant 168 (basf) (in a 1:1 combination by weight): 0.6 parts; ; lubricant PETS (niter) and ethylene acrylic acid copolymerized metal salt ionomer a-C540 (ganivill) (in a 1:1 combination by weight): 0.4 parts.
Adding the raw materials with the formula amount into a mixer, mixing for 15min at 100 r/min, then melting, mixing and shearing the uniformly mixed materials through double screws, extruding, drawing and granulating through a machine head to obtain the PC/PET/POK alloy material capable of being molded in a gas-assisted mode. Wherein, the set temperature of each section of the extruder temperature is as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
Example 4
The embodiment provides a PC/PET/POK alloy material capable of being molded in a gas-assisted mode and a preparation method thereof, wherein the alloy material comprises the following raw materials in parts by weight: the PC resin was Makrolon cube ET3113 (covestro, melt index at 300 ℃ C./1.2 kg of 6.5 g/10 min): 76 parts; PET resin is CH-610 (Shanghai Shangzhi, intrinsic viscosity 0.800.+ -. 0.015 dl/g)): 10 parts; the POK resin was M630A (Korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg: 5.6. 5.6 g/10 min): 10 parts; compatibilizing agent MBS E920 (SK): 3 parts; antioxidant 1076 (basf) and antioxidant P-EPQ (basf) (combined in weight ratio 1:1): 0.6 parts; ; lubricant PETS (niter) and ethylene acrylic acid copolymerized metal salt ionomer a-C540 (ganivill) (in a 1:1 combination by weight): 0.4 parts.
Adding the raw materials with the formula amount into a mixer, mixing for 15min at 100 r/min, then melting, mixing and shearing the uniformly mixed materials through double screws, extruding, drawing and granulating through a machine head to obtain the PC/PET/POK alloy material capable of being molded in a gas-assisted mode. Wherein, the extruder temperature is as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
Example 5
The embodiment provides a PC/PET/POK alloy material capable of being molded in a gas-assisted mode and a preparation method thereof, wherein the alloy material comprises the following raw materials in parts by weight: PC 2558/kesi (melt index at 300 ℃/1.2 kg is 15.5 g/10 min): 76 parts; PET resin is CH-610 (Shanghai Shangzhan, intrinsic viscosity 0.800+ -0.015 dl/g): 10 parts; the POK resin was M630A (Korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg: 5.6. 5.6 g/10 min): 10 parts; compatibilizing agent POK-g-GMA (homemade): 3 parts; antioxidant 1076 (basf) and antioxidant P-EPQ (basf) (combined in weight ratio 1:1): 0.6 parts; lubricant PETS (niter) and ethylene acrylic acid copolymerized metal salt ionomer a-C540 (ganivill) (in a 1:1 combination by weight): 0.4 parts.
Adding the raw materials with the formula amount into a mixer, mixing for 15min at 100 r/min, then melting, mixing and shearing the uniformly mixed materials through double screws, extruding, drawing and granulating through a machine head to obtain the PC/PET/POK alloy material capable of being molded in a gas-assisted mode. Wherein, the extruder temperature is as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
Example 6
The embodiment provides a PC/PET/POK alloy material capable of being molded in a gas-assisted mode and a preparation method thereof, wherein the alloy material comprises the following raw materials in parts by weight: the PC resin was Makrolon cube ET3113 (covestro, melt index at 300 ℃ C./1.2 kg of 6.5 g/10 min): 76 parts; PET resin is CH-610 (Shanghai Shangzhan, intrinsic viscosity 0.800+ -0.015 dl/g): 10 parts; POK resin was M930F (Korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg 60 g/10 min): 10 parts; compatibilizing agent POK-g-GMA (homemade): 3 parts; antioxidant 1076 (basf) and antioxidant P-EPQ (basf) (combined in weight ratio 1:1): 0.6 parts; lubricant PETS (niter) and ethylene acrylic acid copolymerized metal salt ionomer a-C540 (ganivill) (in a 1:1 combination by weight): 0.4 parts.
Adding the raw materials with the formula amount into a mixer, mixing for 15min at 100 r/min, then melting, mixing and shearing the uniformly mixed materials through double screws, extruding, drawing and granulating through a machine head to obtain the PC/PET/POK alloy material capable of being molded in a gas-assisted mode. Wherein, the extruder temperature is as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
Example 7
The embodiment provides a PC/PET/POK alloy material capable of being molded in a gas-assisted mode and a preparation method thereof, wherein the alloy material comprises the following raw materials in parts by weight: the PC resin was Makrolon cube ET3113 (covestro, melt index at 300 ℃ C./1.2 kg of 6.5 g/10 min): 76 parts; PET resin is CH-610 (Shanghai Shangzhan, intrinsic viscosity 0.800+ -0.015 dl/g): 10 parts; the POK resin was M630A (Korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg: 5.6. 5.6 g/10 min): 10 parts; POK-g-GMA/Ionic liquid A (homemade): 3 parts; antioxidant 1076 (basf) and antioxidant P-EPQ (basf) (combined in weight ratio 1:1): 0.6 parts; lubricant PETS (niter) and ethylene acrylic acid copolymerized metal salt ionomer a-C540 (ganivill) (in a 1:1 combination by weight): 0.4 parts.
Adding the raw materials with the formula amount into a mixer, mixing for 15min at 100 r/min, then melting, mixing and shearing the uniformly mixed materials through double screws, extruding, drawing and granulating through a machine head to obtain the PC/PET/POK alloy material capable of being molded in a gas-assisted mode. Wherein, the extruder temperature is as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
Example 8
The embodiment provides a PC/PET/POK alloy material capable of being molded in a gas-assisted mode and a preparation method thereof, wherein the alloy material comprises the following raw materials in parts by weight: the PC resin was Makrolon cube ET3113 (covestro, melt index at 300 ℃ C./1.2 kg of 6.5 g/10 min): 73 parts; PET resin is CH-610 (Shanghai Shangzhan, intrinsic viscosity 0.800+ -0.015 dl/g): 8 parts; the POK resin was M630A (Korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg: 5.6. 5.6 g/10 min): 15 parts; compatibilizing agent POK-g-GMA/ionic liquid A (homemade): 3 parts; antioxidant 1010 (basf) and antioxidant 168 (basf) (in a 1:1 combination by weight): 0.6 parts; lubricant PETS (niter) and ethylene acrylic acid copolymerized metal salt ionomer a-C540 (ganivill) (in a 1:1 combination by weight): 0.4 parts.
Adding the raw materials with the formula amount into a mixer, mixing for 15min at 100 r/min, then melting, mixing and shearing the uniformly mixed materials through double screws, extruding, drawing and granulating through a machine head to obtain the PC/PET/POK alloy material capable of being molded in a gas-assisted mode. Wherein, the extruder temperature is as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
Example 9
The embodiment provides a PC/PET/POK alloy material capable of being molded in a gas-assisted mode and a preparation method thereof, wherein the alloy material comprises the following raw materials in parts by weight: the PC resin was Makrolon cube ET3113 (covestro, melt index at 300 ℃ C./1.2 kg of 6.5 g/10 min): 76 parts; PET resin is CH-610 (Shanghai Shangzhan, intrinsic viscosity 0.800+ -0.015 dl/g): 10 parts; the POK resin was M630A (Korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg: 5.6. 5.6 g/10 min): 10 parts; POK-g-GMA/Ionic liquid B (homemade): 3 parts; antioxidant 1076 (basf) and antioxidant P-EPQ (basf) (combined in weight ratio 1:1): 0.6 parts; lubricant PETS (niter) and ethylene acrylic acid copolymerized metal salt ionomer a-C540 (ganivill) (in a 1:1 combination by weight): 0.4 parts.
Adding the raw materials with the formula amount into a mixer, mixing for 15min at 100 r/min, then melting, mixing and shearing the uniformly mixed materials through double screws, extruding, drawing and granulating through a machine head to obtain the PC/PET/POK alloy material capable of being molded in a gas-assisted mode. Wherein, the extruder temperature is as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
Comparative example 1
Comparative example 1: the PC/PET/POK alloy material capable of being molded in a gas-assisted mode and the preparation method thereof are provided, and the alloy material comprises the following raw materials in parts by weight: PC is Makrolon ET3113 (covestro, melt index at 300 ℃/1.2 kg 6.5 g/10 min): 61 parts; PET resin is CH-610 (Shanghai Shangzhi, intrinsic viscosity 0.800.+ -. 0.015 dl/g)): 8 parts; the POK resin was M630A (Korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg: 5.6. 5.6 g/10 min): 25 parts; compatibilizing agent POK-g-GMA (homemade): 5 parts; antioxidant 1076 (basf) and antioxidant P-EPQ (basf) (combined in weight ratio 1:1): 0.6 parts; ; lubricant PETS (niter) and ethylene acrylic acid copolymerized metal salt ionomer a-C540 (ganivill) (in a 1:1 combination by weight): 0.4 parts.
Adding the raw materials with the formula amount into a mixer, mixing for 15min at 100 r/min, then melting, mixing and shearing the uniformly mixed materials through double screws, extruding, drawing and granulating through a machine head to obtain the PC/PET/POK alloy material capable of being molded in a gas-assisted mode. Wherein, the set temperature of each section of the extruder temperature is as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
Comparative example 2
Comparative example 1: the PC/PET/POK alloy material capable of being molded in a gas-assisted mode and the preparation method thereof are provided, and the alloy material comprises the following raw materials in parts by weight: the PC resin was Makrolon cube ET3113 (covestro, melt index at 300 ℃ C./1.2 kg of 6.5 g/10 min): 61 parts; PET resin is CH-610 (Shanghai Shangzhan, intrinsic viscosity 0.800+ -0.015 dl/g): 25 parts; the POK resin was M630A (Korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg: 5.6. 5.6 g/10 min): 10 parts; compatibilizing agent POK-g-GMA (homemade): 3 parts; antioxidant 1010 (basf) and antioxidant 168 (basf) (in a 1:1 combination by weight): 0.6 parts; ; lubricant PETS (niter) and ethylene acrylic acid copolymerized metal salt ionomer a-C540 (ganivill) (in a 1:1 combination by weight): 0.4 parts.
Adding the raw materials with the formula amount into a mixer, mixing for 15min at 100 r/min, then melting, mixing and shearing the uniformly mixed materials through double screws, extruding, drawing and granulating through a machine head to obtain the PC/PET/POK alloy material capable of being molded in a gas-assisted mode. Wherein, the set temperature of each section of the extruder temperature is as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
Comparative example 3
Comparative example 1: the PC/PET/POK alloy material capable of being molded in a gas-assisted mode and the preparation method thereof are provided, and the alloy material comprises the following raw materials in parts by weight: PC is Makrolon ET3113 (covestro, melt index at 300 ℃/1.2 kg 6.5 g/10 min): 80 parts; PET resin is CH-610 (Shanghai Shangzhi, intrinsic viscosity 0.800.+ -. 0.015 dl/g)): 10 parts; the POK resin was M630A (Korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg: 5.6. 5.6 g/10 min): 6 parts; compatibilizing agent POK-g-GMA (homemade): 3 parts; antioxidant 1076 (basf) and antioxidant P-EPQ (basf) (combined in weight ratio 1:1): 0.6 parts; ; lubricant PETS (niter) and ethylene acrylic acid copolymerized metal salt ionomer a-C540 (ganivill) (in a 1:1 combination by weight): 0.4 parts.
Adding the raw materials with the formula amount into a mixer, mixing for 15min at 100 r/min, then melting, mixing and shearing the uniformly mixed materials through double screws, extruding, drawing and granulating through a machine head to obtain the PC/PET/POK alloy material capable of being molded in a gas-assisted mode. Wherein, the extruder temperature is as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
Comparative example 4
The comparative example provides a PC/PET/POK alloy material capable of being molded in a gas-assisted mode and a preparation method thereof, wherein the alloy material comprises the following raw materials in parts by weight: the PC resin was Makrolon cube ET3113 (covestro, melt index at 300 ℃ C./1.2 kg of 6.5 g/10 min): 76 parts; PET resin is CH-610 (Shanghai Shangzhan, intrinsic viscosity 0.800+ -0.015 dl/g): 10 parts; the POK resin was M630A (Korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg: 5.6. 5.6 g/10 min): 10 parts; compatibilizing agent PE-g-GMA (AX 8840) (SK): 3 parts; antioxidant 1010 (basf) and antioxidant 168 (basf) (in a 1:1 combination by weight ratio): 0.6 parts; ethylene bisstearamide ACRAWAX C (EBS LONZA) and erucamide Crodamide ER (CRODA) (combined in weight ratio 1:1): 0.4 parts.
Adding the raw materials with the formula amount into a mixer, mixing for 15min at 100 r/min, then melting, mixing and shearing the uniformly mixed materials through double screws, extruding, drawing and granulating through a machine head to obtain the PC/PET/POK alloy material capable of being molded in a gas-assisted mode. Wherein, the extruder temperature is as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
Comparative example 5
The comparative example provides a PC/PET/POK alloy material capable of being molded in a gas-assisted mode and a preparation method thereof, wherein the alloy material comprises the following raw materials in parts by weight: the PC resin was Makrolon cube ET3113 (covestro, melt index at 300 ℃ C./1.2 kg of 6.5 g/10 min): 71 parts; PET resin is CH-610 (Shanghai Shangzhan, intrinsic viscosity 0.800+ -0.015 dl/g): 15 parts; the POK resin was M630A (Korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg: 5.6. 5.6 g/10 min): 10 parts; compatibilizing agent MBS (E920) (SK): 3 parts; antioxidant 1010 (basf) and antioxidant 168 (basf) (in a 1:1 combination by weight): 0.6 parts; ethylene bisstearamide ACRAWAX C (EBS LONZA) and erucamide Crodamide ER (CRODA) (combined in weight ratio 1:1): 0.4 parts.
Adding the raw materials with the formula amount into a mixer, mixing for 15min at 100 r/min, then melting, mixing and shearing the uniformly mixed materials through double screws, extruding, drawing and granulating through a machine head to obtain the PC/PET/POK alloy material capable of being molded in a gas-assisted mode. Wherein, the extruder temperature is as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
Comparative example 6
The embodiment provides a PC/PET/POK alloy material capable of being molded in a gas-assisted mode and a preparation method thereof, wherein the alloy material comprises the following raw materials in parts by weight: the PC resin was Makrolon cube ET3113 (covestro, melt index at 300 ℃ C./1.2 kg of 6.5 g/10 min): 76 parts; PET resin is CH-610 (Shanghai Shangzhan, intrinsic viscosity 0.800+ -0.015 dl/g): 10 parts; the POK resin was M630A (Korean phosphor, melt index at 240 ℃ C./1.2: 1.2 kg: 5.6. 5.6 g/10 min): 10 parts; compatibilizer PET-g-GMA (homemade): 3 parts; antioxidant 1076 (basf) and antioxidant P-EPQ (basf) (combined in weight ratio 1:1): 0.6 parts; lubricant PETS (niter) and ethylene acrylic acid copolymerized metal salt ionomer a-C540 (ganivill) (in a 1:1 combination by weight): 0.4 parts.
Adding the raw materials with the formula amount into a mixer, mixing for 15min at 100 r/min, then melting, mixing and shearing the uniformly mixed materials through double screws, extruding, drawing and granulating through a machine head to obtain the PC/PET/POK alloy material capable of being molded in a gas-assisted mode. Wherein, the extruder temperature is as follows: 200-220 ℃, 210-230 ℃, 230-260 ℃, 220-250 ℃, 210-230 ℃, 230-230 ℃ and die temperature 230-260 ℃; the double screw rotating speed of the double screw extruder is 400r/min.
| Tensile Strength (MPa) | Flexural Strength (MPa) | Flexural modulus (MPa) | Notched impact strength (kJ/. Square meter) | Tensile strength retention (double 85/1000 h) | Melt index (280 ℃/2.16 kg) | Transmittance (%) | |
| Test standard | ISO527 | ISO178 | ISO178 | ISO179 | ISO 188 &ISO527 | ISO113 | ASTM D1003 (thickness 3 mm) |
| Example 1 | 58 | 90 | 2515 | 45 | 82% | 7.5 | 91% |
| Example 2 | 55 | 84 | 2300 | 44 | 83% | 9 | 88% |
| Example 3 | 56.5 | 87 | 2460 | 42 | 83% | 11 | 86% |
| Example 4 | 57 | 87 | 2430 | 46 | 78% | 7.5 | 90% |
| Example 5 | 55 | 86 | 2345 | 46 | 74% | 13 | 82% |
| Example 6 | 52 | 86 | 2467 | 36 | 82% | 15 | 80% |
| Example 7 | 62 | 94 | 2741 | 49 | 86% | 7.4 | 92% |
| Example 8 | 60 | 92 | 2630 | 48 | 87% | 8.8 | 90% |
| Example 9 | 61 | 92 | 2691 | 49 | 87% | 14.2 | 90% |
| Comparative example 1 | 53 | 80 | 2150 | 38 | 85% | 20 | 83% |
| Comparative example 2 | 55 | 88 | 2568 | 35 | 80% | 15 | 83% |
| Comparative example 3 | 60 | 92 | 2650 | 50 | 68% | 5.3 | 85% |
| Comparative example 4 | 52 | 83 | 2250 | 46 | 75% | 6.3 | 85% |
| Comparative example 5 | 54 | 85 | 2320 | 47 | 73% | 7 | 84% |
| Comparative example 6 | 54 | 82 | 2186 | 45 | 77% | 6.5 | 86% |
From the results of the examples and comparative examples, it can be seen that:
from examples 1-4, it is clear that when the compatibilizer is POK-g-GMA, different PET and POK contents have an effect on notched impact, flexural strength and modulus, wherein when the POK content is high, the flexural strength and modulus of the material are reduced; when the PET content is high, the melt index becomes high and the notched impact decreases.
As is clear from examples 1 to 6, controlling the melt indexes of the PC resin and the POK resin within a specific range can further improve the light transmittance;
From examples 1-2 and examples 7-9, it is known that when the compatibilizer system contains an ionic liquid, the tensile strength, bending modulus and notched impact strength of the alloy material can be improved simultaneously;
As can be seen from examples 1, 7 and 9, when the content of the ionic liquid in the compatibilizer system is increased, the tensile strength, bending modulus and notched impact strength of the alloy material can be increased to some extent, but the melt flow rate of the alloy material is excessively fast;
From examples 1 to 3, comparative examples 1 and 3 show that when the PC content is increased, the tensile strength, flexural strength, modulus and impact strength are all improved, but the hydrolysis resistance is deteriorated, and it is presumed that the ester group of the PC molecular chain is easily hydrolyzed at high temperature, resulting in a decrease in strength; when the PET and POK contents are certain; when the content of POK and PET increases, the fluidity increases, presumably because POK and PET are crystalline materials, and when the temperature reaches the melting point, the materials are sufficiently melted and become very easy to flow, but the fluidity is too high, which is unfavorable for the processing production of gas-assist molding, and the materials need to maintain a certain melt strength in the molten state.
As is clear from examples 1 to 3 and comparative examples 2 to 6, the selection of the compatibilizing agent has an effect on the tensile strength, flexural modulus, notched impact strength and light transmittance of the alloy material of the present invention, and the selection of POK-g-GMA and POK-g-GMA/ionic liquid of the present invention can provide alloy materials having more excellent overall properties.
In summary, according to the PC/PET/POK alloy material capable of being molded in a gas-assisted manner and the preparation method thereof, the PC/PET/POK alloy material capable of being molded in a gas-assisted manner with excellent comprehensive performance is prepared through the optimized combination proportion of PC, PET, POK and compatilizer.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (7)
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