CN116496610A - PET modified material and preparation method and application thereof - Google Patents
PET modified material and preparation method and application thereof Download PDFInfo
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- CN116496610A CN116496610A CN202310770270.XA CN202310770270A CN116496610A CN 116496610 A CN116496610 A CN 116496610A CN 202310770270 A CN202310770270 A CN 202310770270A CN 116496610 A CN116496610 A CN 116496610A
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- 239000000463 material Substances 0.000 title claims abstract description 342
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 292
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 292
- 239000003365 glass fiber Substances 0.000 claims abstract description 69
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 33
- 239000000155 melt Substances 0.000 claims abstract description 33
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 32
- 239000000945 filler Substances 0.000 claims abstract description 25
- 238000006068 polycondensation reaction Methods 0.000 claims description 44
- 239000008188 pellet Substances 0.000 claims description 41
- 239000003963 antioxidant agent Substances 0.000 claims description 39
- 239000007790 solid phase Substances 0.000 claims description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 239000002667 nucleating agent Substances 0.000 claims description 33
- 239000011265 semifinished product Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- 229910021389 graphene Inorganic materials 0.000 claims description 30
- 230000003078 antioxidant effect Effects 0.000 claims description 26
- 239000012745 toughening agent Substances 0.000 claims description 25
- 239000000314 lubricant Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000011231 conductive filler Substances 0.000 claims description 17
- 238000001125 extrusion Methods 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- 229910052787 antimony Inorganic materials 0.000 claims description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- YKIBJOMJPMLJTB-UHFFFAOYSA-M sodium;octacosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O YKIBJOMJPMLJTB-UHFFFAOYSA-M 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical class OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 3
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- UTOPWMOLSKOLTQ-UHFFFAOYSA-M octacosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O UTOPWMOLSKOLTQ-UHFFFAOYSA-M 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920000120 polyethyl acrylate Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 17
- 238000012360 testing method Methods 0.000 description 40
- 230000017525 heat dissipation Effects 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 230000002829 reductive effect Effects 0.000 description 19
- 238000005452 bending Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 11
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound 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 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
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002671 adjuvant Substances 0.000 description 5
- 230000002411 adverse Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 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 2
- 239000003921 oil Substances 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 238000007676 flexural strength test Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 210000003128 head Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001052 transient effect Effects 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application provides a PET modified material, and a preparation method and application thereof. The PET modified material comprises the following components in percentage by mass: 45-90 wt% of polyethylene terephthalate, 0-20 wt% of heat conducting filler, 1.3-6.4 wt% of auxiliary agent and 7-50 wt% of glass fiber; wherein the melt index of the PET modified material is 10g/10 min-20 g/10min. The PET modified material has higher molecular weight, and is beneficial to improving the mechanical property of the PET modified material.
Description
Technical Field
The application relates to the technical field of automobiles, in particular to a PET modified material and a preparation method and application thereof.
Background
At present, with the continuous development of technology, heat dissipation materials are required in many fields. Because of the limitations of weight and processability, metals, ceramics and other materials with excellent heat conducting properties are difficult to meet the requirements of modern industry, and plastic products with relatively light mass and easy processing become ideal heat dissipation materials.
Polyethylene terephthalate (Polyethylene glycol terephthalate, PET) can be widely used as a heat dissipation material in the automotive field, such as a high-voltage box shell, a FUSE (FUSE) base, an automotive modularized lamp module or a heat-conducting lamp bracket of a new energy automobile, due to excellent mechanical properties, heat resistance, electrical properties and chemical stability. However, with the rapid development of technology, higher demands are put forward on the heat dissipation performance and mechanical properties of the heat dissipation material, and at present, many properties of the PET material cannot meet the high demands of the modern emerging industry due to the limitation of the manufacturing process.
Disclosure of Invention
The present invention has been made in view of the above problems, and an object thereof is to provide a PET-modified material having a low melt index, having significantly enhanced mechanical properties, and satisfying the demands of the modern and emerging industries.
In a first aspect of the present application, a PET-modified material is provided, and the preparation of the PET-modified material includes the following components in percentage by mass:
45-90 wt% of polyethylene terephthalate,
0-20 wt% of heat conducting filler,
1.3-6.4 wt% of auxiliary agent,
7-50 wt% of glass fiber;
the melt index of the PET modified material is 10g/10 min-20 g/10min.
Polyethylene terephthalate (PET) is used as a base material, and the heat conducting filler, the auxiliary agent, the glass fiber and the PET react to prepare the PET modified material, and the melt index of the PET modified material is controlled to be 10g/10 min-20 g/10min, so that the PET modified material has larger molecular weight, and the mechanical property of the PET modified material is improved.
In any embodiment, the PET-modified material has a viscosity greater than 0.65dl/g. In any embodiment, the PET-modified material has a viscosity greater than 0.85dl/g.
The viscosity of the PET modified material is controlled to be more than 0.65dl/g, so that the PET modified material has larger molecular weight, and is beneficial to the improvement of mechanical properties.
In any embodiment, the polyethylene terephthalate comprises a homopolyethylene terephthalate.
The homo-polyethylene terephthalate has a regular molecular structure, is favorable for improving the crystallinity of the PET modified material, and further improves the mechanical property of the PET modified material.
In any embodiment, the thermally conductive filler comprises one or more of graphene flakes, natural graphite, carbon nanotubes, carbon fibers, thermally conductive carbon materials, boron nitride, aluminum nitride, silicon carbide, aluminum oxide, magnesium oxide, optionally comprising graphene flakes.
The addition of the heat conducting filler is beneficial to improving the heat conductivity coefficient of the PET modified material, namely the heat dissipation performance of the PET modified material is obviously improved.
In any embodiment, the preparation of the PET-modified material comprises the following components in percentage by mass:
45-90 wt% of polyethylene terephthalate,
1-20wt% of flaky graphene,
1.3-6.4 wt% of auxiliary agent,
7-50 wt% of glass fiber.
The flaky graphene has a planar carbon six-membered ring conjugated crystal structure, has a larger radial width/thickness ratio and a large contact area, so that the heat conductivity of the PET modified material can be remarkably improved, and the heat dissipation performance of the PET modified material is greatly improved.
In any embodiment, the auxiliary agent comprises a toughening agent, a nucleating agent, a lubricant, and an antioxidant, optionally the auxiliary agent further comprises an antimony-containing compound.
The auxiliary agent can comprehensively improve the toughness, crystallinity, processability and oxidation resistance of the PET modified material.
In any embodiment, the mass fraction of the toughening agent is 1wt% to 5wt% based on the total mass of the PET-modified material.
In any embodiment, the toughening agent comprises one or more of ethylene methyl acrylate-glycidyl methacrylate copolymer, polymethyl acrylate, polyethyl acrylate, copolymerized polyethylene terephthalate, olefin copolymer elastomer, polyether ester.
The toughening agent can effectively improve the toughness of the PET modified material and reduce the risk of impact resistance reduction caused by cracking of the PET modified material under external impact. The mass fraction of the toughening agent is controlled within a proper range, so that the toughness of the PET modified material can be effectively improved, and adverse effects on the PET modified material caused by the degradation of excessive toughening agent at high temperature can be avoided.
In any embodiment, the nucleating agent is 0.1wt% to 0.35wt% based on the total mass of the PET-modified material.
In any embodiment, the nucleating agent comprises one or more of an organic nucleating agent comprising one or more of sodium montanate, sorbitol salt, benzoate salt, P250, surlyn8920, RS-735, and an inorganic nucleating agent comprising one or more of talc, barium sulfate.
The nucleating agent can be used as crystallization sites of PET modified materials, so that the PET modified materials have proper crystallinity, and the mechanical properties of the PET modified materials are improved. The mass fraction of the nucleating agent is controlled within a proper range, so that enough nucleating sites are provided to enable the PET modified material to be a crystal substance, the mechanical property of the PET modified material is improved, and the influence of the introduction of excessive nucleating agent on the performance of the PET modified material can be reduced.
In any embodiment, the lubricant is present in an amount of 0.1wt% to 0.5wt% based on the total mass of the PET-modified material.
In any embodiment, the lubricant comprises one or more of silicone powder, silicone masterbatch, polyethylene wax, stearate, montanate.
The lubricant can improve the processability of PET modified materials. The mass fraction of the lubricant is controlled in a proper range, so that the processing performance of the PET modified material can be effectively improved, and the influence of the introduction of excessive lubricant on the performance of the PET modified material can be reduced.
In any embodiment, the antioxidant is present in an amount of 0.1wt% to 0.5wt% based on the total mass of the PET-modified material.
In any embodiment, the antioxidant comprises one or more of a hindered phenolic antioxidant comprising one or more of antioxidant 1010, antioxidant 2246, antioxidant 1076, antioxidant 330, and a phosphite antioxidant comprising one or more of antioxidant 168, antioxidant 626, antioxidant 619, antioxidant 3010, antioxidant PEP 36.
The antioxidant can improve the oxidation resistance of the PET modified material. The mass fraction of the antioxidant is controlled in a proper range, so that the oxidation resistance of the PET modified material can be effectively improved, and the influence of the introduction of excessive antioxidant on the performance of the PET modified material can be reduced.
In any embodiment, the glass fibers comprise one or more of alkali-free long glass fibers, alkali-free short glass fibers, optionally alkali-free short glass fibers.
The alkali-free long glass fiber or the alkali-free short glass fiber can effectively improve the mechanical properties of the PET modified material.
In any embodiment, the diameter of the alkali-free short glass fiber is 7 um-13 um, optionally 7 um-10 um, and the fiber length of the alkali-free short glass fiber is 3 mm-6 mm, optionally 3 mm-4.5 mm.
The diameter and the fiber length of the alkali-free short glass fiber are controlled within proper ranges, so that the mechanical property of the PET modified material can be effectively improved, and the load on production equipment caused by the introduction of the glass fiber can be reduced.
The second aspect of the present application provides a method for preparing a PET-modified material, the raw materials for preparing the PET-modified material include:
45-90 wt% of polyethylene terephthalate,
0-20 wt% of heat conducting filler,
1.3-6.4 wt% of auxiliary agent,
7-50 wt% of glass fiber;
the melt index of the PET modified material is 10g/10 min-20 g/10min.
The PET modified material is prepared by reacting the heat conducting filler, the auxiliary agent, the glass fiber and the PET, and the melt index of the PET modified material is controlled to be 10g/10 min-20 g/10min, so that the PET modified material has larger molecular weight, and the mechanical property of the PET modified material is improved.
In any embodiment, the auxiliary agent comprises a toughening agent, a nucleating agent, a lubricant, and an antioxidant, optionally the auxiliary agent further comprises an antimony-containing compound.
The toughening agent is beneficial to improving the toughness of the PET modified material, so that the impact resistance of the PET material is improved. The nucleating agent is used as a nucleating site of the PET modified material, which is favorable for forming crystalline substances and improving the mechanical property of the PET modified material. The addition of the lubricant is beneficial to improving the fluidity of the PET modified material in the preparation process, and can be quickly demoulded, thereby shortening the preparation period. The antioxidant is beneficial to improving the oxidation resistance of the PET modified material. The antimony-containing compound can further accelerate the reaction rate of the PET modified material and shorten the production time.
In any embodiment, the method of making comprises:
mixing and processing the raw materials to prepare a PET modified material pellet semi-finished product;
and carrying out solid-phase polycondensation reaction on the PET modified material pellet semi-finished product to obtain the PET modified material.
The molecular weight of the PET modified material can be improved through solid phase polycondensation reaction of the PET modified material pellet semi-finished product, namely the melt index of the PET modified material is further reduced, the viscosity is further improved, and the mechanical property of the PET modified material is improved.
In any embodiment, the gas atmosphere of the solid phase polycondensation reaction is a nitrogen atmosphere, and the vacuum degree of the solid phase polycondensation reaction is lower than 50Pa.
In any embodiment, the reaction temperature of the solid phase polycondensation reaction is 165-245 ℃, optionally 225-235 ℃, and the reaction time is 8-15 h, optionally 8-12 h.
The solid phase polycondensation reaction is controlled to react under proper conditions, so that the molecular weight of the PET modified material is improved, namely the melt index of the PET modified material is further reduced, the viscosity is further improved, and the mechanical property of the PET modified material is improved.
In any embodiment, the preparation method specifically includes:
putting polyethylene glycol terephthalate and the auxiliary agent into a mixer to be mixed to obtain a premix; optionally, the premix further comprises the thermally conductive filler;
Adding the premix and the glass fiber into an extruder, processing, extruding and granulating to obtain a PET modified material pellet semi-finished product;
and (3) carrying out solid-phase polycondensation reaction on the PET modified material pellet semi-finished product in a nitrogen atmosphere under the vacuum degree lower than 50Pa, wherein the reaction temperature is 165-245 ℃ and the reaction time is 8-15 h, and thus the PET modified material is obtained.
The PET modified material pellet semi-finished product is further subjected to solid phase polycondensation reaction, so that the molecular weight of the PET modified material is further improved, namely the melt index of the PET modified material is further reduced, the viscosity is further improved, and the mechanical property of the PET modified material is improved.
In any embodiment, the extrusion temperature of the extruder is 260-290 ℃, and the rotation speed of the extruder is 300-450 rmp.
The extrusion temperature and the rotating speed of the extruder are controlled in proper ranges, so that the raw materials can be fully mixed and reacted, and adverse effects of the excessive temperature or the excessive rotating speed on the PET modified material pellet semi-finished product can be reduced.
In any embodiment, the step of adding the premix and the glass fibers to an extruder to process and extrude pellets, and the step of preparing the PET modified material pellet semi-finished product comprises the following steps:
Adding the premix through a main feeding port of an extruder;
adding the glass fiber through a side feeding port of an extruder;
the extrusion temperature of the extruder is controlled to be 260-290 ℃, and the rotating speed of the extruder is 300-450 rmp, so that the PET modified material pellet semi-finished product is prepared.
The premix and the glass fiber are added into an extruder through different feeding ports, so that the premix and the glass fiber are uniformly mixed and fully reacted.
In any embodiment, the pellet semi-finished PET-modified material has a viscosity greater than 0.5dl/g, alternatively greater than 0.65dl/g.
In any embodiment, the viscosity of the PET-modified material is greater than 0.65dl/g, optionally greater than 0.85dl/g.
The viscosity of the PET modified material is obviously greater than that of the PET modified material pellet semi-finished product, namely the molecular weight of the PET modified material is obviously greater than that of the PET modified material pellet semi-finished product, and the mechanical property of the PET modified material is improved.
In a third aspect of the present application, there is provided the use of the PET-modified material of the first aspect or the PET-modified material prepared by the preparation method of the second aspect in an automobile.
Drawings
Fig. 1 is a scanning electron microscope image of a PET-modified material according to an embodiment of the present application.
Fig. 2 is a partial enlarged view of fig. 1.
Detailed Description
Embodiments of PET-modified materials, methods of producing the same, and applications of the same are specifically disclosed below in detail with reference to the accompanying drawings as appropriate. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the drawings and the following description are provided for a full understanding of the present application by those skilled in the art, and are not intended to limit the subject matter recited in the claims.
The "range" disclosed herein is defined in terms of lower and upper limits, with a given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, unless specifically stated otherwise.
All technical features and optional technical features of the present application may be combined with each other to form new technical solutions, unless specified otherwise.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise indicated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
Reference herein to "comprising" and "including" means open ended, as well as closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
Generally, an auxiliary agent and a PET matrix are adopted for melt blending to prepare the PET material, but the PET material generally has overlarge melt index and overlarge melt strength, and the mechanical property of the PET material does not meet the requirements of products on the market, so that a PET modified material needs to be provided to meet the requirements of modern emerging industries.
[ PET-modified Material ]
Based on the above, the application provides a PET modified material, which comprises the following components in percentage by mass:
45-90 wt% of polyethylene terephthalate,
0-20 wt% of heat conducting filler,
1.3-6.4 wt% of auxiliary agent,
7-50 wt% of glass fiber;
wherein the melt index of the PET modified material is 10g/10 min-20 g/10min.
Herein, the sum of the mass fraction of polyethylene terephthalate, the mass fraction of the thermally conductive filler, the mass fraction of the auxiliary agent and the mass fraction of the glass fiber is 100% based on the total mass of the PET-modified material.
As used herein, the term "adjuvant" refers to a substance that can improve the properties of PET-modified materials, including but not limited to toughening agents, nucleating agents, lubricants, or antioxidants.
In some embodiments, the mass fraction of polyethylene terephthalate may be selected to be 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, or a value in a range consisting of any two points described above, the mass fraction of thermally conductive filler may be selected to be 0wt%, 1wt%, 2wt%, 4wt%, 5wt%, 6wt%, 8wt%, 10wt%, 12wt%, 14wt%, 15wt%, 16wt%, 18wt%, 20wt%, or a value in a range consisting of any two points described above, the mass fraction of the auxiliary agent may be selected to be 1.3wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5.5wt%, 6wt%, 6.4wt%, or a value in a range consisting of any two points described above, and the mass fraction of glass fiber may be selected to be 7wt%, 8wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 40wt%, or a value in a range consisting of any two points described above.
In some embodiments, the PET-modified material has a melt index of 10g/10min, 11g/10min, 12g/10min, 13g/10min, 14g/10min, 15g/10min, 16g/10min, 17g/10min, 18g/10min, 19g/10min, 20g/10min, or a value in the range consisting of any two of the foregoing.
In this context, the melt index and the molecular weight of the PET-modified material are inversely related. The smaller the melt index of the PET-modified material, the greater its molecular weight. The improvement of the molecular weight of the PET modified material is beneficial to the improvement of the mechanical property of the PET modified material.
In this context, the melt index of the PET-modified material may be tested using any known method. As an example, the melt index of the PET-modified material was tested with reference to test standard ISO 1133. About 20g of PET modified material is taken and baked in a baking oven at 150 ℃ for 1h, and is added into a melt index tester while the PET modified material is hot, and the PET modified material is tested according to the test temperature of 300 ℃ and the mass of 2.16kg to obtain the melt index in g/10min.
Polyethylene terephthalate (PET) is used as a base material, and the heat conducting filler, the auxiliary agent, the glass fiber and the PET react to prepare the PET modified material, and the melt index of the PET modified material is controlled to be 10g/10 min-20 g/10min, so that the PET modified material has larger molecular weight, and the mechanical property of the PET modified material is improved.
In some embodiments, the viscosity of the PET-modified material is greater than 0.65dl/g, optionally greater than 0.85dl/g.
In some embodiments, the viscosity of the PET-modified material may be selected to be 0.655dl/g, 0.66dl/g, 0.686dl/g, 0.70dl/g, 0.72dl/g, 0.74dl/g, 0.75dl/g, 0.76dl/g, 0.78dl/g, 0.8dl/g, 0.85dl/g, 0.9dl/g, 0.95dl/g, 1.0dl/g, 1.05dl/g, or a value in the range consisting of any two points described above.
In this context, the viscosity and molecular weight of the PET-modified material are in a positive correlation. The greater the viscosity of the PET-modified material, the greater its molecular weight. The improvement of the molecular weight of the PET modified material is beneficial to the improvement of the mechanical property of the PET modified material.
In this context, the viscosity of the PET-modified material may be tested using any known method. As an example, a viscosity test of PET modified materials was performed with reference to test standard GB/T14190-2008. A Ubbelohde viscometer method is adopted, and a viscosity tube with the diameter of 0.84mm is adopted. The solvent is prepared by mixing phenol and tetrachloroethane according to a volume ratio of 1:1, and preparing 500ml for standby. 200mg of PET modified material is put into a 25ml volumetric flask, mixed solvent with the volume of 2/3 is added, then the volumetric flask is put into a constant-temperature oil bath pot with the temperature of 130 ℃ for about 2-3 hours until the PET modified material is completely dissolved in the solvent, the PET modified material is taken out and cooled to the room temperature of 25 ℃ after being completely dissolved by naked eyes, and then the volume is fixed to 25ml by adopting the prepared solvent. The dissolved glass fibers in the PET-modified material were then filtered off using a buchner funnel. The viscosity was measured in dl/mg using the filtered PET-modified material solution.
The viscosity of the PET modified material is controlled to be more than 0.65dl/g, so that the PET modified material has larger molecular weight, and is beneficial to the improvement of mechanical properties.
In some embodiments, the polyethylene terephthalate comprises a homopolyethylene terephthalate.
The homo-polyethylene terephthalate has a regular molecular structure, is favorable for improving the crystallinity of the PET modified material, and further improves the mechanical property of the PET modified material.
In some embodiments, the thermally conductive filler comprises one or more of graphene flakes, natural graphite, carbon nanotubes, carbon fibers, thermally conductive carbon materials, boron nitride, aluminum nitride, silicon carbide, aluminum oxide, magnesium oxide, optionally comprising graphene flakes.
Herein, the term "graphene flakes" refers to a single-layer graphene layered stack having a carbon number of more than 10 and a thickness in the range of 5 to 100 nm. The flake graphene has an ultrathin structure. The flaky graphene maintains the original planar carbon six-membered ring conjugated crystal structure of the single-layer graphene, and still has excellent mechanical strength, heat conduction performance, and good lubrication, high temperature resistance and corrosion resistance.
The addition of the heat conducting filler is beneficial to improving the heat conductivity coefficient of the PET modified material, namely the heat dissipation performance of the PET modified material is obviously improved.
In some embodiments, preparing the PET-modified material comprises the following components in mass percent:
45-90 wt% of polyethylene terephthalate,
1-20wt% of flaky graphene,
1.3-6.4 wt% of auxiliary agent,
7-50 wt% of glass fiber.
In some embodiments, the mass fraction of the graphene flakes may be selected to be 0wt%, 1wt%, 2wt%, 4wt%, 5wt%, 6wt%, 8wt%, 10wt%, 12wt%, 14wt%, 15wt%, 16wt%, 18wt%, 20wt%, or a value in a range consisting of any two points above, based on the total mass of the PET-modified material.
The flaky graphene has a planar carbon six-membered ring conjugated crystal structure, the thickness of the flaky graphene is in the nano-size range, the radial width of the flaky graphene can reach the micron level, and the contact area of the flaky graphene can be increased due to the large ratio of the radial width to the thickness of the flaky graphene, so that the heat conductivity of the PET modified material can be remarkably improved, and the heat dissipation performance of the PET modified material is greatly improved.
In some embodiments, the adjuvants include toughening agents, nucleating agents, lubricants, and antioxidants, optionally, the adjuvants further include antimony-containing compounds.
The auxiliary agent can comprehensively improve the toughness, crystallinity, processability and oxidation resistance of the PET modified material.
In some embodiments, the mass fraction of the toughening agent is 1wt% to 5wt% based on the total mass of the PET-modified material. In some embodiments, the mass fraction of the toughening agent may be selected to be 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, or a value in the range consisting of any two points above, based on the total mass of the PET modified material.
In some embodiments, the toughening agent includes one or more of ethylene methyl acrylate-glycidyl methacrylate copolymer, polymethyl acrylate, polyethyl acrylate, copolymerized polyethylene terephthalate, olefin copolymer elastomer, polyether ester.
In this context, the mass content of Glycidyl Methacrylate (GMA) in the ethylene-methyl acrylate-glycidyl methacrylate copolymer is 6% to 10%, and the mass content of ethylene or methyl acrylate in the ethylene-methyl acrylate-glycidyl methacrylate copolymer is not limited.
The toughening agent can effectively improve the toughness of the PET modified material and reduce the risk of impact resistance reduction caused by cracking of the PET modified material under external impact. The mass fraction of the toughening agent is controlled within a proper range, so that the toughness of the PET modified material can be effectively improved, and adverse effects on the PET modified material caused by the degradation of excessive toughening agent at high temperature can be avoided.
In some embodiments, the mass fraction of the nucleating agent is 0.1wt% to 0.35wt% based on the total mass of the PET-modified material. In some embodiments, the mass fraction of the nucleating agent may be selected to be 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt%, or a value in the range consisting of any two points above, based on the total mass of the PET-modified material.
In some embodiments, the nucleating agent comprises one or more of an organic nucleating agent comprising one or more of sodium montanate, sorbitol salt, benzoate salt, P250, surlyn8920, RS-735, and an inorganic nucleating agent comprising one or more of talc, barium sulfate.
The nucleating agent can be used as crystallization sites of PET modified materials, so that the PET modified materials have proper crystallinity, and the mechanical properties of the PET modified materials are improved. The mass fraction of the nucleating agent is controlled within a proper range, so that enough nucleating sites are provided to enable the PET modified material to be a crystal substance, the mechanical property of the PET modified material is improved, and the influence of the introduction of excessive nucleating agent on the performance of the PET modified material can be reduced.
In some embodiments, the mass fraction of lubricant is 0.1wt% to 0.5wt% based on the total mass of the PET-modified material. In some embodiments, the mass fraction of lubricant may be selected to be 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt%, 0.4wt%, 0.45wt%, 0.5wt%, or a value in the range consisting of any two points above, based on the total mass of the PET-modified material.
In some embodiments, the lubricant comprises one or more of silicone powder, silicone masterbatch, polyethylene wax, stearate, montanate.
The lubricant can improve the processability of PET modified materials. The mass fraction of the lubricant is controlled in a proper range, so that the processing performance of the PET modified material can be effectively improved, and the influence of the introduction of excessive lubricant on the performance of the PET modified material can be reduced.
In some embodiments, the antioxidant is 0.1wt% to 0.5wt% based on the total mass of the PET-modified material. In some embodiments, the mass fraction of antioxidant may be selected to be 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt%, 0.4wt%, 0.45wt%, 0.5wt%, or a value in the range consisting of any two of the foregoing, based on the total mass of the PET-modified material.
In some embodiments, the antioxidants include one or more of hindered phenolic antioxidants, phosphite antioxidants, including one or more of antioxidant 1010, antioxidant 2246, antioxidant 1076, antioxidant 330, and phosphite antioxidants, including one or more of antioxidant 168, antioxidant 626, antioxidant 619, antioxidant 3010, antioxidant PEP 36.
The antioxidant can improve the oxidation resistance of the PET modified material. The mass fraction of the antioxidant is controlled in a proper range, so that the oxidation resistance of the PET modified material can be effectively improved, and the influence of the introduction of excessive antioxidant on the performance of the PET modified material can be reduced.
In some embodiments, the antimony-containing compound includes one or more of sodium antimonate, antimony trioxide, ethylene glycol antimony, antimony acetate, antimony trichloride.
In some embodiments, the glass fibers comprise one or more of alkali-free long glass fibers, alkali-free short glass fibers, optionally alkali-free short glass fibers.
The alkali-free long glass fiber or the alkali-free short glass fiber can effectively enhance the mechanical property of the PET modified material.
In some embodiments, the diameter of the alkali-free short glass fibers is 7um to 13um, optionally 7um to 10um, and the fiber length of the alkali-free short glass fibers is 3mm to 6mm, optionally 3mm to 4.5mm. In some embodiments, the diameter of the alkali-free staple glass fiber may be selected to be 7um, 8um, 9um, 10um, 11um, 12um, 13um, or a value in the range consisting of any two of the foregoing, and the fiber length of the alkali-free staple glass fiber may be selected to be 3mm, 3.5mm, 4mm, 4.5mm, 5mm, 5.5mm, 6mm, or a value in the range consisting of any two of the foregoing.
The diameter and the fiber length of the alkali-free short glass fiber are controlled within proper ranges, so that the mechanical property of the PET modified material can be effectively improved, and the load on production equipment caused by the introduction of the glass fiber can be reduced.
The application also provides a preparation method of the PET modified material, which comprises the following raw materials:
45-90 wt% of polyethylene terephthalate,
0-20 wt% of heat conducting filler,
1.3-6.4 wt% of auxiliary agent,
7-50 wt% of glass fiber;
wherein the melt index of the PET modified material is 10g/10 min-20 g/10min.
The PET modified material is prepared by reacting the heat conducting filler, the auxiliary agent, the glass fiber and the PET, and the melt index of the PET modified material is controlled to be 10g/10 min-20 g/10min, so that the PET modified material has larger molecular weight, and the mechanical property of the PET modified material is improved. The heat-conducting filler can improve the heat dissipation performance of the PET modified material, improve the crystallization temperature of the PET modified material, shorten the manufacturing period of the PET modified material and improve the production efficiency.
In some embodiments, the adjuvants include toughening agents, nucleating agents, lubricants, and antioxidants, optionally, the adjuvants further include antimony-containing compounds.
The toughening agent is beneficial to improving the toughness of the PET modified material, so that the impact resistance of the PET material is improved. The nucleating agent is used as a nucleating site of the PET modified material, which is favorable for forming crystalline substances and improving the mechanical property of the PET modified material. The addition of the lubricant is beneficial to improving the fluidity of the PET modified material in the preparation process, and can be quickly demoulded, thereby shortening the preparation period. The antioxidant is beneficial to improving the oxidation resistance of the PET modified material. The antimony-containing compound can further accelerate the reaction rate of the PET modified material and shorten the production time.
In some embodiments, the method of making comprises:
mixing and processing the raw materials to prepare a PET modified material pellet semi-finished product;
and (3) carrying out solid-phase polycondensation reaction on the PET modified material pellet semi-finished product to obtain the PET modified material.
As used herein, the term "solid phase polycondensation" refers to polycondensation of molten polyethylene terephthalate having a lower molecular weight in a pellet semi-finished product of PET-modified material under vacuum and high temperature conditions, such that the molecular weight of the PET-modified material is increased, i.e., the melt index is decreased. The polycondensation reaction can be a polycondensation reaction between low molecular weight polyethylene terephthalate with terminal carboxyl groups and diethylene glycol, or a polycondensation reaction between low molecular weight polyethylene terephthalate with terminal carboxyl groups or terminal hydroxyl groups, and the solid phase polycondensation reaction has the advantages of low reaction temperature, less side reaction, low acetaldehyde content and excellent product performance.
It can be understood that the conventional preparation method of PET material only comprises the steps of mixing and reacting PET modified material with heat conducting filler and auxiliary agent at high temperature, extruding, and the melt index is generally larger, the molecular weight is lower, and the mechanical property is lower. In the embodiment of the application, the PET modified material pellet semi-finished product is subjected to solid phase polycondensation reaction, so that the molecular weight of the PET modified material can be improved, namely, the melt index of the PET modified material is further reduced, the viscosity is further improved, and the mechanical property of the PET modified material is improved.
In addition, the addition of the heat conducting filler can obviously improve the heat conductivity coefficient of the PET modified material, namely, the addition of the heat conducting filler can lead the PET modified material to have excellent heat dissipation performance, but the addition of the heat conducting filler can generally cause the reduction of the mechanical performance of the PET modified material, which is not beneficial to the mechanical performance of the PET modified material. In the embodiment of the application, the mixed and processed PET modified material pellet semi-finished product is further subjected to solid phase polycondensation reaction, the molecular weight of the PET modified material is improved, namely, the melt index of the PET modified material is further reduced, the viscosity is further improved, and the mechanical property of the PET modified material is improved.
In some embodiments, the gas atmosphere of the solid phase polycondensation reaction is a nitrogen atmosphere, and the vacuum degree of the solid phase polycondensation reaction is less than 50Pa.
In some embodiments, the reaction temperature of the solid phase polycondensation reaction is 165 ℃ to 245 ℃, optionally 225 ℃ to 235 ℃, and the reaction time is 8 hours to 15 hours, optionally 8 hours to 12 hours. In some embodiments, the reaction temperature of the solid phase polycondensation reaction may be selected to be 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, or a value in the range consisting of any two points described above, and the reaction time may be selected to be 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, or a value in the range consisting of any two points described above.
It can be understood that the solid phase polycondensation reaction is a reversible reaction, and the vacuum degree, the reaction time and the reaction temperature of the solid phase polycondensation reaction are controlled within proper ranges, so that the forward progress of the polycondensation reaction is facilitated, the molecular weight of the PET modified material is improved, namely, the melt index of the PET modified material is further reduced, the viscosity is further improved, and the mechanical property of the PET modified material is improved. Meanwhile, the solid phase polycondensation reaction is also beneficial to reducing the content of carboxyl groups at the end of the PET modified material, so that the hydrolysis resistance of the PET modified material can be effectively improved, and the performance of the PET modified material is comprehensively improved.
In addition, the vacuum degree of the solid phase polycondensation reaction is controlled to be lower than 50Pa, which is also beneficial to the gasification and the pumping of a large amount of low molecular weight substances (such as micromolecular substances, diethylene glycol and water molecules generated by the decomposition of the toughening agent and the nucleating agent at high temperature) under the vacuum, so that the PET modified material has low volatile matter content.
In some embodiments, the method of preparation specifically comprises:
putting polyethylene glycol terephthalate and an auxiliary agent into a mixer to be mixed so as to obtain a premix; optionally, the premix further comprises a thermally conductive filler;
adding the premix and the glass fiber into an extruder, processing, extruding and granulating to obtain a PET modified material pellet semi-finished product;
and (3) carrying out solid-phase polycondensation reaction on the PET modified material pellet semi-finished product in a nitrogen atmosphere under the vacuum degree lower than 50Pa, wherein the reaction temperature is 165-245 ℃ and the reaction time is 8-15 h, and thus the PET modified material is obtained.
The PET modified material pellet semi-finished product is further subjected to solid phase polycondensation reaction, so that the molecular weight of the PET modified material is further improved, namely the melt index of the PET modified material is further reduced, the viscosity is further improved, and the mechanical property of the PET modified material is improved.
In some embodiments, the extruder has an extrusion temperature of 260 ℃ to 290 ℃ and a rotational speed of 300rmp to 450rmp. In some embodiments, the extruder has an extrusion temperature of 260 ℃, 265 ℃, 270 ℃, 275 ℃, 280 ℃, 285 ℃, 290 ℃, or a value in the range consisting of any two points described above, and the extruder has a speed of 300rmp, 320rmp, 340rmp, 350rmp, 360rmp, 380rmp, 400rmp, 420rmp, 440rmp, 450rmp, or a value in the range consisting of any two points described above.
In this context, the vacuum degree of the extruder head is controlled below 0.08MPa, and low molecular weight substances (such as ethanol, oxalic acid, diglycol, carboxyl end group, terephthalic acid or water molecules) which do not participate in the reaction in the premix can be initially gasified and pumped away under vacuum, so that the accumulation of the low molecular weight substances can be reduced to influence the performance of the PET modified material.
The extrusion temperature and the rotating speed of the extruder are controlled in proper ranges, so that the raw materials can be fully mixed and reacted, and adverse effects of the excessive temperature or the excessive rotating speed on the PET modified material pellet semi-finished product can be reduced.
In some embodiments, the step of adding the premix and glass fibers to an extruder to process the extruded pellets to produce a pellet semi-finished PET-modified material comprises:
adding premix through a main feeding port of the extruder;
adding glass fiber through a side feeding port of the extruder;
the extrusion temperature of the extruder is controlled to be 260-290 ℃, and the rotating speed of the extruder is 300-450 rmp, so that the PET modified material pellet semi-finished product is prepared.
The premix and the glass fiber are added into an extruder through different feeding ports, so that the premix and the glass fiber are uniformly mixed and fully reacted.
The extrusion temperature of the extruder is controlled within a proper range, so that the reaction between the premix and the glass fiber can be caused, and the decomposition of the premix caused by the excessively high temperature can be avoided, thereby generating adverse effects. The extrusion rotating speed of the extruder is controlled within a proper range, so that the requirement of uniform stirring can be met, and damage to the PET modified material pellet semi-finished product caused by excessive extrusion rotating speed can be avoided, for example, excessive shearing force can be generated by excessive extrusion rotating speed to act on the premix and the glass fiber, and the premix is easily decomposed into small molecules, so that the performance of the PET modified material pellet semi-finished product is not facilitated.
In some embodiments, the pellet semi-finished PET-modified material has a viscosity greater than 0.5dl/g, optionally greater than 0.65dl/g.
In some embodiments, the viscosity of the PET-modified material is greater than 0.65dl/g, optionally greater than 0.85dl/g.
The viscosity of the PET modified material is obviously greater than that of the PET modified material pellet semi-finished product, namely the molecular weight of the PET modified material is obviously greater than that of the PET modified material pellet semi-finished product, and the mechanical property of the PET modified material is improved.
The present application also provides for the use of the PET-modified material of some embodiments or the PET-modified material prepared by the preparation method of some embodiments in automobiles.
The PET modified material with excellent heat dissipation performance and mechanical property can be widely applied to the field of automobiles, in particular to the field of new energy automobiles, for example, the PET modified material is applied to a high-voltage box shell, a FUSE base, an automobile modularized lamp module or a heat conducting lamp support of the new energy automobile, and due to the excellent heat dissipation performance and mechanical property, the PET modified material can not only meet the heat dissipation requirement of the new energy automobile, but also reduce the thermal runaway risk caused by the fact that heat cannot be timely diffused, and can also meet the requirement of the new energy automobile on mechanical strength, so that the PET modified material has certain impact resistance. In addition, the PET modified material has low volatile content and hydrolysis resistance, so that the service life of the PET modified material can be effectively prolonged, and the PET modified material is applied to the field of new energy automobiles, such as a modularized car lamp module and a heat-conducting car lamp bracket.
Examples
Hereinafter, embodiments of the present application are described. The embodiments described below are exemplary only for the purpose of illustrating the present application and are not to be construed as limiting the present application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
1. Preparation method
Example 1
Preparation of PET modified material
Polyethylene terephthalate, toughening agent ethylene/methyl acrylate/glycidyl methacrylate, nucleating agent sodium montanate, lubricant silicone powder, sodium antimonate, antioxidant 168 and antioxidant 1010 (the mass ratio of the antioxidant 168 to the antioxidant 1010 is 1:1) are put into a high-speed mixer to be uniformly mixed to obtain premix according to the mass ratio of 64:1:0.15:0.2:0.05:0.2.
The premix is added through a main feed of a double-screw extruder, the short glass fiber is added through a side feed of the double-screw extruder (the mass ratio of the glass fiber to the premix is 65.6:34.4), the vacuum degree of a machine head of the double-screw extruder is controlled below 0.08MPa, the extrusion temperature of the double-screw extruder is controlled at 280 ℃, and the screw rotating speed of the double-screw extruder is controlled at 390RPM, so that the PET modified material pellet semi-finished product is prepared.
Subsequently, the PET-modified material pellet semi-finished product is transferred to a tackifying and solidifying machine for solid phase polycondensation. Controlling the temperature in the tackifying and rotating-fixing machine to rise to 120 ℃, and introducing inert gas to discharge water vapor and oxygen in the tackifying and rotating-fixing machine; continuously controlling the temperature in the tackifying and rotating-fixing machine to rise to 150 ℃ and stopping the introduction of inert gas; continuously controlling the temperature in the tackifying and rotating-fixing machine to rise to 230 ℃, controlling the pressure of the tackifying and rotating-fixing machine to be 20Pa, performing solid-phase polycondensation, and stopping the reaction when the melt index of the product in the tackifying and rotating-fixing machine is less than 20g/10min to obtain the PET modified material.
Example 2
The preparation method of the PET modified material in the embodiment 2 is basically similar to the preparation method of the embodiment 1, but the heat-conducting filler flaky graphene is added into the premix, the mass content of polyethylene terephthalate in the PET modified material is adjusted, the mass content of other auxiliary agents is unchanged, and specific parameters are shown in the table 1.
Example 3
The preparation method of the PET modified material in the embodiment 3 is basically similar to the preparation method of the embodiment 2, but the mass content of the heat-conducting filler flaky graphene in the premix and the mass content of the polyethylene terephthalate in the PET modified material are adjusted, and the mass content of other auxiliary agents is unchanged, and specific parameters are shown in the table 1.
Example 4
The preparation method of the PET modified material in the example 4 is basically similar to the example 2, but the flake graphene of the heat conducting filler in the premix is adjusted to magnesium oxide of the heat conducting filler, and specific parameters are shown in the table 1.
Example 5
The preparation method of the PET modified material in the example 5 is basically similar to the example 3, but the flake graphene of the heat conducting filler in the premix is adjusted to magnesium oxide of the heat conducting filler, and specific parameters are shown in the table 1.
Examples 6 to 10
The preparation method of the PET modified material in examples 6 to 10 is basically similar to example 2, but the pressure, reaction temperature and reaction time of solid phase polycondensation in the preparation method of the PET modified material are adjusted, and specific parameters are shown in Table 1.
Comparative example 1
The preparation method of the PET modified material in comparative example 1 is substantially similar to example 1, but the preparation method of the PET modified material does not include a solid phase polycondensation reaction, specifically:
polyethylene terephthalate, toughening agent ethylene/methyl acrylate/glycidyl methacrylate, nucleating agent sodium montanate, lubricant silicone powder, sodium antimonate, antioxidant 168 and antioxidant 1010 (the mass ratio of the antioxidant 168 to the antioxidant 1010 is 1:1) are put into a high-speed mixer to be uniformly mixed to obtain premix according to the mass ratio of 64:1:0.15:0.2:0.05:0.2.
The premix is added through a main feed of a double-screw extruder, the short glass fiber is added through a side feed of the double-screw extruder (the mass ratio of the glass fiber to the premix is 65.6:34.4), the vacuum degree of a machine head of the double-screw extruder is controlled below 0.08MPa, the extrusion temperature of the double-screw extruder is controlled at 280 ℃, and the screw rotating speed of the double-screw extruder is controlled at 350RPM, so that the PET modified material is obtained.
Comparative example 2
The preparation method of the PET modified material in comparative example 2 is basically similar to that of comparative example 1, but the content of other components in the PET modified material is adjusted by adding the heat-conducting filler flaky graphene into the premix, and specific parameters are shown in table 1.
Comparative example 3
The preparation method of the PET modified material in comparative example 3 is basically similar to that of comparative example 2, but the content of the heat conductive filler flake graphene in the premix and the content of other components in the PET modified material are adjusted, and specific parameters are shown in Table 1.
Comparative example 4
The preparation method of the PET modified material in comparative example 4 is basically similar to that of comparative example 2, but the flake graphene of the heat conductive filler in the premix is adjusted to magnesium oxide of the heat conductive filler, and specific parameters are shown in Table 1.
Comparative example 5
The preparation method of the PET modified material in comparative example 5 is basically similar to that of comparative example 3, but the flake graphene of the heat conductive filler in the premix is adjusted to magnesium oxide of the heat conductive filler, and specific parameters are shown in Table 1.
2. Performance testing
1. PET modified material performance test
1) Melt Flow Rate (MFR) test
Reference is made to test standard ISO 1133. About 20g of PET modified material is taken and baked in a baking oven at 150 ℃ for 1h, and is added into a melt index tester while the PET modified material is hot, and the melt index is measured according to the test temperature of 300 ℃ and the mass of 2.16kg, wherein the unit is g/10min.
2) Viscosity test
Reference is made to test standard GB/T14190-2008. A Ubbelohde viscometer method is adopted, and a viscosity tube with the diameter of 0.84mm is adopted. The solvent is prepared by mixing phenol and tetrachloroethane according to a volume ratio of 1:1, and preparing 500ml for standby. 200mg of PET modified material is put into a 25ml volumetric flask, mixed solvent with the volume of 2/3 is added, then the volumetric flask is put into a constant-temperature oil bath pot with the temperature of 130 ℃ for about 2-3 hours until the PET modified material is completely dissolved in the solvent, the PET modified material is taken out and cooled to the room temperature of 25 ℃ after being completely dissolved by naked eyes, and then the volume is fixed to 25ml by adopting the prepared solvent. The dissolved glass fibers in the PET-modified material were then filtered off using a buchner funnel. The viscosity of the filtered PET-modified material solution was measured in dl/mg.
3) Thermal conductivity testing
Reference transient plane method test-reference test standard ASTM D5470. The diameter and thickness of the PET modified material injection molded sample piece used for the injection molding machine are 30mm multiplied by 2mm, and the PET modified material injection molded sample piece is tested by a TH-91-13-00654 heat conductivity coefficient meter of C-Therm company of Canada. The unit of thermal conductivity is W/(m.K)
4) Tensile Strength test
Reference is made to test standard ISO 527. The method comprises the steps of utilizing an injection molding machine to inject a type 1a standard spline (the gauge length of the type 1a spline is 50+/-0.5 mm, the distance between clamps is 115+/-5 mm) by adopting a PET modified material, adopting a tensile strength test by adopting a universal testing machine, and stretching to the maximum tensile strength of the broken material, wherein the tensile strength is the tensile strength of the PET modified material, and the unit is Mpa.
5) Elongation at break test
Reference is made to test standard ISO 527. Injecting a type 1a standard spline (the gauge length of the type 1a spline is 50+/-0.5 mm, the distance between clamps is 115+/-5 mm) by using an injection molding machine through adopting PET modified materials, testing the tensile strength by using a universal testing machine, testing the tensile speed by 10mm/min, installing a testing elongation clamping device, enabling a sample to be positioned on the vertical plane of an upper clamp and a lower clamp, and finely adjusting the position of the upper clamp to enable the sample to be completely straightened but not stressed; measuring the distance between the upper and lower clamps at this time using a vernier caliper-record L 0 Elongation in gauge length at break of sample, i.e. the travel-log DeltaL read at break b Elongation at break Σ= Δl b /L 0 X 100 in%.
6) Flexural Strength test
Reference is made to test standard ISO 178. The standard spline (the spline length is 80mm plus or minus 2mm, the width is 10.0mm plus or minus 0.2mm, and the thickness is 4.0mm plus or minus 0.2 mm) is injection molded by an injection molding machine, a universal testing machine is used for testing bending strength, the bending speed is 2mm/min, a three-point load is applied, a sample is placed on two fulcrums, the load is applied to the centers of the fulcrums, the pressure applied to the sample in the process is measured, and the bending stress when the load reaches the maximum value is the bending strength in Mpa.
7) Flexural modulus test
Reference is made to test standard ISO 178. The standard spline (the spline length is 80mm plus or minus 2mm, the width is 10.0mm plus or minus 0.2mm, and the thickness is 4.0mm plus or minus 0.2 mm) is injection molded by an injection molding machine, a universal testing machine is used for testing bending strength, the bending speed is 2mm/min, a three-point load is applied to the sample, the sample is placed on two fulcrums, the load is applied to the center of each fulcrums, the pressure applied to the sample in the process is measured, the bending stress when the load reaches the maximum value is measured, and the bending modulus is obtained by bending strain generated by bending on the bending stress ratio, and the unit is Mpa.
8) Unnotched impact (simply supported beam) test
Reference is made to test standard ISO 179. The Charpy non-notch impact strength test is carried out by using an injection molding machine to inject standard sample strips (the sample strip length is 80mm plus or minus 2mm, the width is 10.0mm plus or minus 0.2mm, and the thickness is 4.0mm plus or minus 0.2 mm), using an impact tester to test, placing a sample at a specified position of a simple beam impact machine, and then using a pendulum bob to freely fall, applying impact bending load to the sample to break the sample. Obtaining impact toughness of material by using ratio of impact energy consumed by unit cross section area of sample and area, and the unit is KJ/m 2 。
9) Crystallization temperature test
Reference is made to test standard ISO 11357-3. Adopting a differential scanning calorimeter, heating the test condition from 30 ℃ to 300 ℃ at a speed of 20 ℃/min in a nitrogen environment, and keeping the temperature for 5min; then cooling from 300 ℃ to 50 ℃ at a speed of 20 ℃/min, and keeping the temperature constant for 5min; then the temperature is increased from 50 ℃ to 300 ℃ at a speed of 20 ℃/min. And (3) carrying out standard peak tip temperature on the exothermic peak in the cooling section to obtain the crystallization temperature in the unit of DEG C.
10 Haze test)
With reference to the standard VW 50181 test, the test uses gravimetric specimens with a required diameter thickness of 80mm x 2mm, and the analytical test is carried out with an atomizer, with haze in ug/g.
11 PET modified material scanning electron microscope image
Dissolving PET modified material by tetrachloroethane solvent at 130 ℃, filtering, washing tetrachloroethane by ethanol, observing the morphology of insoluble matters after filtering and washing by a scanning electron microscope, and mainly observing the morphology of glass fiber and glass fiber surface resin.
3. Analysis of test results for examples and comparative examples
Batteries of each example and comparative example were prepared according to the above-described methods, and each performance parameter was measured, and the results are shown in tables 1 and 2 below.
TABLE 1
TABLE 2
According to the results, the melt index of the PET modified material in examples 1-10 is 10g/10 min-20 g/10min, and the PET modified material has excellent heat dissipation performance and mechanical properties.
As can be seen from fig. 1 and 2, the polyethylene terephthalate component and the thermal conductive filler component for preparing the PET modified material in the embodiment of the application are in contact with the glass fiber component in a large amount, and form chemical bonds, so that the mechanical properties of the PET modified material can be remarkably improved.
As can be seen from the comparison of the embodiment 1 with the comparative example 1, the embodiment 2, the embodiment 7 to the embodiment 10, the embodiment 3 with the comparative example 3, the embodiment 4 with the comparative example 4, and the embodiment 5 with the comparative example 5, the melt index of the PET modified material is controlled to be 10g/10min to 20g/10min, which is beneficial to improving the tensile strength, the bending modulus and the non-notch impact force (simple beam) of the PET modification.
As can be seen from the comparison of examples 1 and 1, examples 2, 7-10, examples 3 and 3, and examples 4 and 4, and examples 5 and 5, the preparation method of the PET modified material comprises a solid phase polycondensation reaction, so that the melt index of the PET modified material is 10g/10 min-20 g/10min, the viscosity is more than 0.65dl/mg, and further, the tensile strength, elongation at break, bending strength, bending modulus, non-defect impact force (simple beam) and thermal conductivity are improved, the haze is reduced, the mechanical property and heat dissipation property of the PET modified material are comprehensively improved, and the application field of the PET modified material is widened.
As can be seen from the comparison between examples 2-5 and example 1, the addition of the heat conductive filler graphene flakes or magnesium oxide can significantly improve the heat conductivity of the PET modified material, improve the heat dissipation performance of the PET modified material, and also improve the crystallization temperature of the PET modified material. As can be seen from comparison of example 2 and example 4, and example 3 and example 5, compared with magnesium oxide as the heat conductive filler, the flake graphene as the heat conductive filler can further improve the heat conductivity of the PET modified material, and improve the heat dissipation performance of the PET modified material to the greatest extent.
As can be seen from examples 2 and 6, the PET modified material has excellent mechanical properties and heat dissipation performance by controlling the vacuum degree of the solid phase polycondensation reaction to be lower than 50 Pa.
As can be seen from examples 2 and 7-10, the PET modified material has excellent mechanical properties and heat dissipation performance by controlling the reaction temperature of the solid phase polycondensation reaction to 165-245 ℃.
From examples 2 and 7-10, it can be seen that the PET modified material has excellent mechanical properties and heat dissipation performance by controlling the reaction time of the solid phase polycondensation reaction to 8-15 hours.
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.
Claims (31)
1. The PET modified material is characterized by comprising the following components in percentage by mass:
45-90 wt% of polyethylene terephthalate,
0-20 wt% of heat conducting filler,
1.3-6.4 wt% of auxiliary agent,
7-50 wt% of glass fiber;
the melt index of the PET modified material is 10g/10 min-20 g/10min.
2. The PET-modified material of claim 1, wherein the viscosity of the PET-modified material is greater than 0.65dl/g.
3. The PET-modified material of claim 2, wherein the viscosity of the PET-modified material is greater than 0.85dl/g.
4. The PET-modified material of claim 1, wherein the polyethylene terephthalate comprises a homo-polyethylene terephthalate.
5. The PET-modified material of claim 1, wherein the thermally conductive filler comprises one or more of graphene flakes, natural graphite, carbon nanotubes, carbon fibers, thermally conductive carbon materials, boron nitride, aluminum nitride, silicon carbide, aluminum oxide, magnesium oxide.
6. The PET-modified material of claim 5, wherein the PET-modified material is prepared from the following components in percentage by mass:
45-90 wt% of polyethylene terephthalate,
1-20wt% of flaky graphene,
1.3-6.4 wt% of auxiliary agent,
7-50 wt% of glass fiber.
7. The PET-modified material of claim 1, wherein the auxiliary agents comprise a toughening agent, a nucleating agent, a lubricant, and an antioxidant.
8. The PET-modified material of claim 7, wherein the auxiliary agent further comprises an antimony-containing compound.
9. The PET-modified material of claim 7, wherein the mass fraction of the toughening agent is 1wt% to 5wt% based on the total mass of the PET-modified material;
the toughening agent comprises one or more of ethylene-methyl acrylate-glycidyl methacrylate copolymer, polymethyl acrylate, polyethyl acrylate, copolymerized polyethylene terephthalate, olefin copolymer elastomer and polyether ester.
10. The PET-modified material of claim 7, wherein the mass fraction of the nucleating agent is 0.1wt% to 0.35wt% based on the total mass of the PET-modified material;
the nucleating agent comprises one or more of an organic nucleating agent and an inorganic nucleating agent, wherein the organic nucleating agent comprises one or more of sodium montanate, sorbitol salt and benzoate, and the inorganic nucleating agent comprises one or more of talcum powder and barium sulfate.
11. The PET-modified material of claim 7, wherein the mass fraction of the lubricant is 0.1wt% to 0.5wt% based on the total mass of the PET-modified material;
the lubricant comprises one or more of silicone powder, silicone master batch, polyethylene wax, stearate and montanate.
12. The PET-modified material according to claim 7, wherein the antioxidant is 0.1wt% to 0.5wt% based on the total mass of the PET-modified material;
the antioxidant comprises one or more of hindered phenol antioxidants and phosphite antioxidants, wherein the hindered phenol antioxidants comprise one or more of antioxidants 1010, 2246, 1076 and 330, and the phosphite antioxidants comprise one or more of antioxidants 168, 626, 619, 3010 and PEP 36.
13. The PET-modified material of any one of claims 1 to 12, wherein the glass fibers comprise one or more of alkali-free long glass fibers, alkali-free short glass fibers.
14. The PET-modified material of any one of claims 1 to 12, wherein the glass fibers comprise alkali-free short glass fibers.
15. The PET-modified material of claim 14, wherein the alkali-free short glass fibers have a diameter of 7um to 13um and a fiber length of 3mm to 6mm.
16. The PET-modified material of claim 15, wherein the alkali-free short glass fibers have a diameter of 7um to 10um and a fiber length of 3mm to 4.5mm.
17. The preparation method of the PET modified material is characterized by comprising the following raw materials:
45-90 wt% of polyethylene terephthalate,
0-20 wt% of heat conducting filler,
1.3-6.4 wt% of auxiliary agent,
7-50 wt% of glass fiber;
the melt index of the PET modified material is 10g/10 min-20 g/10min.
18. The method of claim 17, wherein the auxiliary agents include toughening agents, nucleating agents, lubricants, and antioxidants.
19. The method of claim 18, wherein the auxiliary agent further comprises an antimony-containing compound.
20. The method of manufacturing according to claim 17, characterized in that the method of manufacturing comprises:
Mixing and processing the raw materials to prepare a PET modified material pellet semi-finished product;
and carrying out solid-phase polycondensation reaction on the PET modified material pellet semi-finished product to obtain the PET modified material.
21. The method according to claim 20, wherein the gas atmosphere of the solid phase polycondensation reaction is a nitrogen atmosphere, and the vacuum degree of the solid phase polycondensation reaction is lower than 50Pa;
the reaction temperature of the solid phase polycondensation reaction is 165-245 ℃ and the reaction time is 8-15 h.
22. The method according to claim 21, wherein the gas atmosphere of the solid phase polycondensation reaction is a nitrogen atmosphere, and the vacuum degree of the solid phase polycondensation reaction is lower than 50Pa;
the reaction temperature of the solid phase polycondensation reaction is 225-235 ℃, and the reaction time is 8-12 h.
23. The preparation method according to claim 20, characterized in that it comprises in particular:
putting polyethylene glycol terephthalate and the auxiliary agent into a mixer to be mixed to obtain a premix;
adding the premix and the glass fiber into an extruder, processing, extruding and granulating to obtain a PET modified material pellet semi-finished product;
and (3) carrying out solid-phase polycondensation reaction on the PET modified material pellet semi-finished product in a nitrogen atmosphere under the vacuum degree lower than 50Pa, wherein the reaction temperature is 165-245 ℃ and the reaction time is 8-15 h, and thus the PET modified material is obtained.
24. The method of making according to claim 23, wherein the premix further comprises the thermally conductive filler.
25. The method according to claim 23, wherein the extrusion temperature of the extruder is 260 ℃ to 290 ℃ and the rotation speed of the extruder is 300rmp to 450rmp.
26. The method of claim 23, wherein the step of adding the premix and the glass fibers to an extruder to process and extrude pellets to produce the semi-finished PET-modified material pellets comprises:
adding the premix through a main feeding port of an extruder;
adding the glass fiber through a side feeding port of an extruder;
the extrusion temperature of the extruder is controlled to be 260-290 ℃, and the rotating speed of the extruder is 300-450 rmp, so that the PET modified material pellet semi-finished product is prepared.
27. The process according to any one of claims 20 to 26, wherein the pellet semi-finished PET-modified material has a viscosity of greater than 0.5dl/g.
28. The process according to claim 27, wherein the pellet semi-finished PET-modified material has a viscosity greater than 0.65dl/g.
29. The method of any one of claims 20 to 26, wherein the PET-modified material has a viscosity of greater than 0.65dl/g.
30. The method of claim 29, wherein the PET-modified material has a viscosity greater than 0.85dl/g.
31. Use of the PET-modified material according to any one of claims 1 to 16 or the PET-modified material prepared by the preparation method according to any one of claims 17 to 30, for automobiles.
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