CN108440924B - Lightweight polyethylene terephthalate with low fluidity and easy processing and preparation method thereof - Google Patents
Lightweight polyethylene terephthalate with low fluidity and easy processing and preparation method thereof Download PDFInfo
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- CN108440924B CN108440924B CN201810314903.5A CN201810314903A CN108440924B CN 108440924 B CN108440924 B CN 108440924B CN 201810314903 A CN201810314903 A CN 201810314903A CN 108440924 B CN108440924 B CN 108440924B
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- 229920000139 polyethylene terephthalate Polymers 0.000 title claims abstract description 123
- 239000005020 polyethylene terephthalate Substances 0.000 title claims abstract description 123
- -1 polyethylene terephthalate Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000003672 processing method Methods 0.000 title description 2
- 239000011324 bead Substances 0.000 claims abstract description 90
- 238000007667 floating Methods 0.000 claims abstract description 89
- 239000004970 Chain extender Substances 0.000 claims abstract description 44
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000012545 processing Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000001125 extrusion Methods 0.000 claims abstract description 32
- 239000000155 melt Substances 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 39
- 238000005469 granulation Methods 0.000 claims description 20
- 230000003179 granulation Effects 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000012986 modification Methods 0.000 claims description 17
- 230000004048 modification Effects 0.000 claims description 17
- 239000008188 pellet Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 9
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 235000006708 antioxidants Nutrition 0.000 claims 4
- 239000003795 chemical substances by application Substances 0.000 claims 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims 1
- 239000003017 thermal stabilizer Substances 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 6
- 229920001223 polyethylene glycol Polymers 0.000 abstract 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 abstract description 6
- 238000013329 compounding Methods 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 description 47
- 239000000203 mixture Substances 0.000 description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000005303 weighing Methods 0.000 description 16
- 238000005406 washing Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000013585 weight reducing agent Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 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 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 7
- 238000005187 foaming Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 238000012216 screening Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 230000007547 defect Effects 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses polyethylene glycol terephthalate with low fluidity and easy processing and lightening and a preparation method thereof. The melt flow rate of the polyethylene terephthalate is 35.3-14.7.0 g/10min, and the intrinsic viscosity is 0.84-1.310 dL/g. The invention prepares the polyethylene glycol terephthalate by adding hollow floating beads modified by the surface of a silane coupling agent, a mixed chain extender formed by compounding a carboxyl addition type chain extender monomer and an isocyanate chain extender monomer, an antioxidant and a heat stabilizer, and extruding and granulating by a screw. The preparation method is simple to operate, the reaction extrusion equipment occupies small space and can continuously produce, and the polyethylene glycol terephthalate prepared by the method has the characteristics of large molecular weight, low fluidity, light weight, easy extrusion of melt and the like.
Description
Technical Field
The invention belongs to the technical field of polyester polymer processing modification, and particularly relates to a preparation method of light polyethylene terephthalate with low fluidity and easy processing.
Background
At present, PET is mainly applied to the fields of films, beverage bottles and fibers in China; the consumption of the engineering plastics is only 1.6 percent of the total consumption of the PET, and the PET engineering plastics in domestic markets are almost all imported. On one hand, because PET is easily degraded by water, heat and oxygen during processing, the molecular weight is reduced, the viscosity is reduced, and the processing and forming are difficult; on the other hand, the application of PET in the field of engineering plastics needs to be further expanded.
At present, the PET chain extension tackifying method comprises the following three methods: melt polycondensation, solid phase polycondensation, and reactive extrusion. The melt polycondensation method is rarely used because of the problems that heat and byproducts are difficult to discharge, and kettle cleaning is difficult. The solid phase polycondensation method generally has low reaction temperature, the molecular weight is obviously improved between Tg and Tm, but the reaction needs to be carried out under the protection of vacuum or inert gas, and the equipment is complex and the cost is high. The reactive extrusion method has the advantages of relatively simple operation, environmental friendliness, obvious chain extension effect, low cost and the like, and is widely adopted. In addition, the reactive extrusion method also comprises condensation type and addition type, and the chain extension effect which can be achieved by adding a chain extender in the reactive extrusion process is certain, on one hand, the functional group for reaction at the tail end of the macromolecular chain is certain; on the other hand, the effect is not obvious by simply increasing the content of the chain extender, even the molecular weight is reduced, and the whole molecular weight is not increased much because the content of the chain extender is too high and the chain extension reaction points are increased. Therefore, the combination of the suitable chain extender is important, and the carboxyl addition type chain extender and the hydroxyl addition type chain extender are combined, so that both ends of the PET can carry out chain extension reaction, and the defect of a single chain extender is overcome. The search for suitable chain extenders for use in combination remains to be explored.
With the progress of science and technology and the development of human society, the energy and environmental problems become more and more prominent, the weight of the foam plastic is lightened to be a new requirement for the material manufacture in various application fields, and the foam plastic is a product which is in line with the development trend. Commonly used foam materials are: PU, PE, PS, etc. Although the application is very wide, the material and the processing method have certain defects. For example, the PU can discharge toxic gas in the processing process, the PE product has poor mechanical property and is not high temperature resistant, and the PS waste is difficult to recycle and easy to cause pollution and the like. For the research on the weight reduction of polyester, chemical foaming and physical foaming are mainly performed, for the chemical foaming, a foaming agent is generally adopted, and gas released by the foaming agent is used for forming foam holes, but because the PET processing temperature is higher, about 250-265 ℃, and higher than the degradation temperature of the foaming agent, the foaming agent cannot be foamed at a proper melt temperature, so that the problems of low porosity, uneven cell size and the like are caused. For physical foaming, a supercritical fluid is mainly diffused into a polymer matrix in a diffusion dissolution mode to form a homogeneous polymer melt/gas solution, and then the system is induced to generate a thermodynamically unstable state by rapidly reducing the pressure of the system or raising the temperature of the system, so that the system is subjected to phase separation to generate bubble nuclei from the homogeneous system. However, physical foaming is also insufficient, for example, the dispersion degree of the dispersed phase is not easy to control, which easily causes uneven cells, the process conditions are harsh, high pressure and low temperature are required, and the foaming cost is high.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects in the prior art are overcome, the lightweight polyethylene glycol terephthalate with low fluidity and easy processing and the preparation method thereof are provided, the defect of tackifying modification of a single chain extender is overcome, the degradation of PET in the processing process is reduced, the molecular weight of the PET is improved, and the fluidity of the PET is reduced; the PET mechanical property is improved, and meanwhile, easy processing and lightweight research are carried out, so that the problems of difficulty in melt extrusion, severe extrusion swelling and obvious particle yellowing caused by deepening of molecular tackifying degree are solved.
In order to solve the technical problems, the invention adopts the technical scheme that:
a low-fluidity and easy-to-process lightweight polyethylene terephthalate is obtained by chain extension through a mixed chain extender and lightweight modification through hollow floating beads modified by the surface of a silane coupling agent.
Further, the low-fluidity and easily-processed lightweight polyethylene terephthalate has a melt flow rate of 35.3 to 14.7g/10min and an intrinsic viscosity of 0.84 to 1.31 dL/g.
A method for preparing the low-fluidity and easily-processed lightweight polyethylene terephthalate comprises the following steps:
(1) carrying out surface modification on the hollow floating bead by using a silane coupling agent;
(2) and (3) drying treatment: respectively drying the surface-modified hollow floating beads and the PET granules to obtain dried surface-modified hollow floating beads and dried PET granules;
(3) fully stirring and uniformly mixing the dried PET granules, the dried surface-modified hollow floating beads, the mixed chain extender, the antioxidant and the heat stabilizer in the step (2) to prepare a mixed material, putting the mixed material into a screw extruder for reaction, extrusion and granulation, and finally preparing the low-fluidity and light-weight polyethylene terephthalate which is easy to process; the mixed chain extender is prepared by compounding a carboxyl addition type chain extender monomer and an isocyanate chain extender monomer.
Further, the particle size of the hollow floating bead in the step (1) is 1-250 μm, and the volume weight is 250-450 kg/m3The mass consumption of the silane coupling agent is 1-10% of the mass consumption of the hollow floating beads, and the particle size of the surface modified hollow floating beads is 60-100 meshes.
Further, the melting point of the PET granules in the step (2) is 250-255 ℃, and the initial intrinsic viscosity is 0.7-0.8 dL/g.
Further, the mass amount of the dried surface-modified hollow floating bead in the step (3) is 10-50% of the mass of the PET granules, the mass amount of the mixed chain extender is 0.2-2.0% of the mass of the PET granules, the mass amount of the antioxidant is 0.1-0.6% of the mass of the PET granules, and the mass amount of the heat stabilizer is 0.1-0.6% of the mass of the PET granules.
Further, the mass ratio of the carboxyl addition type chain extender monomer to the isocyanate type chain extender monomer in the mixed chain extender in the step (3) is 1: 9-9: 1.
Further, the carboxyl addition type chain extender in the step (3) is any one of 1, 4-butanediol diglycidyl ether (BDE for short), l, 6-hexanediol diglycidyl ether (HDE for short), ethylene glycol diglycidyl ether (GDE for short) and triglycidyl isocyanurate (TGIC for short); the isocyanate chain extender is any one of 1, 4-Phenylene Diisocyanate (PDI), 4, 4-diphenylmethane diisocyanate (MDI) and Hexamethylene Diisocyanate (HDI).
Further, the antioxidant in the step (3) is any one of antioxidant 1010 and antioxidant CA, and the heat stabilizer is any one of trimethyl phosphate (TMP for short), triphenyl phosphate (TPP for short) and triethyl phosphonoacetate (TEPA for short).
Further, the screw extruder in the step (3) is a double screw extruder, the first zone temperature of the double screw extruder is 120-180 ℃, the second zone temperature of the double screw extruder is 140-180 ℃, the third zone temperature of the double screw extruder is 160-210 ℃, the fourth zone temperature of the double screw extruder is 200-260 ℃, the fifth zone temperature of the double screw extruder is 230-260 ℃, the sixth zone temperature of the double screw extruder is 240-280 ℃, the seventh zone temperature of the double screw extruder is 240-280 ℃, the eighth zone temperature of the double screw extruder is 250-280 ℃, the ninth zone temperature of the double screw extruder is 250-280 ℃ and the head temperature of the double screw extruder; the feeding frequency of the double-screw extruder is 5-20 Hz, and the rotating frequency of the main machine is 5-20 Hz.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
Compared with the prior art, the invention has the following technical effects:
(1) the carboxyl addition type chain extender and the isocyanate chain extender are combined, the using effect of the combined chain extender is better than that of a single chain extender under the condition of a certain adding amount of the chain extender, the melt flow rate under the combination is obviously reduced, the minimum melt flow rate is 14.7.0g/10min, and the melt flow rate is reduced by 81.5 percent compared with pure PET; the intrinsic viscosity is increased from 0.70dL/g to 1.31dL/g, and the intrinsic viscosity is increased by 87.1 percent; not only improves the processing performance of PET, but also reduces the using amount of expensive chain extender and reduces the cost.
(2) The invention also expands the application of PET in weight reduction, abandons the defects that a chemical foaming agent is not high-temperature resistant, the physical foaming condition is harsh, the critical gas is not easy to control and the like, tries to fill the hollow floating bead with a surface modification, has simple operation, not only plays a role in weight reduction, but also can reduce the processing difficulty, and can cause the problems of difficult melt extrusion, serious extrusion swelling, obvious granular material yellowing and the like along with the deepening of the molecular tackifying degree.
(3) The reaction extrusion process adopted by the invention has the advantages of less reaction extrusion equipment, less occupied space and simple operation, and can realize continuous production; the reaction can realize the control of temperature and time, thereby controlling the quality of the product; and the energy consumption is low, the processing and modification cost can be reduced, no waste is discharged, and the environment is not polluted.
Detailed Description
The following specific examples illustrate the present invention in detail, but the present invention is not limited to the following examples:
(example 1)
A preparation method of polyethylene terephthalate with low fluidity and easy processing and weight reduction comprises the following steps:
(1) carrying out surface modification on the hollow floating bead by using a silane coupling agent: firstly, the particle size is 1-250 μm, and the volume weight is 250-450 kg/m3Weighing a silane coupling agent with the mass being 1% of that of the hollow floating beads in a beaker, preparing the silane coupling agent into an ethanol water solution with the concentration of 1%, adjusting the pH value of the silane coupling agent to 1 by using acetic acid with the mass ratio of the ethanol to the water being 5:1, stirring the mixture at room temperature for 0.5 hour to fully hydrolyze the silane coupling agent, then putting the weighed hollow floating beads into the beaker, carrying out ultrasonic treatment for 0.5 hour to uniformly mix the hollow floating beads, placing the mixture in a 40 ℃ water bath kettle, carrying out mechanical stirring reaction for 1 hour, then taking the mixture out, cooling the mixture to room temperature, carrying out repeated suction filtration and washing on the surface-modified hollow floating bead solution, drying the material after washing, then slightly grinding the dried material, and screening the surface-modified hollow floating beads with the particle size of 60 meshes for later use.
(2) And (3) drying treatment: drying the surface-modified hollow floating bead in the step (1) in an oven at 90 ℃ for 5 hours to obtain a dried surface-modified hollow floating bead; and (3) drying the PET granules with the melting point of 250-255 ℃ and the initial intrinsic viscosity of 0.7-0.8 dL/g in a forced air oven at 100 ℃ for 8h, transferring the PET granules into a vacuum oven, and drying the PET granules in vacuum at 100 ℃ for 8h to obtain the dried PET granules.
(3) And (3) reaction extrusion granulation: weighing 800g of dried PET granules, 80g of dried surface-modified hollow floating beads, 0.16g of BDE, 1.44g of PDI, 0.8g of antioxidant 1010 and 0.8g of TEPA, fully stirring and uniformly mixing to prepare a mixed material; and then putting the mixed material into a screw extruder for reaction extrusion and granulation, and adjusting the temperature of each area of the double screws as follows: the first zone is 120 ℃, the second zone is 140 ℃, the third zone is 160 ℃, the fourth zone is 200 ℃, the fifth zone is 230 ℃, the sixth zone is 240 ℃, the seventh zone is 240 ℃, the eighth zone is 250 ℃, the ninth zone is 250 ℃, the head is 250 ℃, the rotation frequency of a double-screw extruder feeder is 5Hz, and the rotation frequency of a main machine is 5Hz, so that the polyethylene terephthalate with low fluidity and easy processing and lightening is finally prepared.
(example 2)
A preparation method of polyethylene terephthalate with low fluidity and easy processing and weight reduction comprises the following steps:
(1) carrying out surface modification on the hollow floating bead by using a silane coupling agent: firstly, the particle size is 1-250 μm, and the volume weight is 250-450 kg/m3Weighing a silane coupling agent with the mass being 2% of that of the hollow floating beads in a beaker, preparing the silane coupling agent into an ethanol water solution with the concentration of 5%, adjusting the mass ratio of ethanol to water to be 6:1, adjusting the pH value to 3 by using acetic acid, stirring for 1 hour at room temperature to fully hydrolyze the silane coupling agent, adding the weighed hollow floating beads, carrying out ultrasonic treatment for 1 hour to uniformly mix the hollow floating beads, placing the mixture in a 50 ℃ water bath kettle for mechanical stirring reaction for 2 hours, taking out the mixture, cooling the mixture to room temperature, repeatedly carrying out suction filtration and washing on the surface-modified hollow floating bead solution, drying the material after washing, slightly grinding the dried material, and screening the surface-modified hollow floating beads with the particle size of 70 meshes for later use.
(2) And (3) drying treatment: drying the surface-modified hollow floating bead in the step (1) in a drying oven at 100 ℃ for 2h to obtain a dried surface-modified hollow floating bead; and (3) drying the PET granules with the melting point of 250-255 ℃ and the initial intrinsic viscosity of 0.7-0.8 dL/g in a forced air oven at 110 ℃ for 9h, transferring the PET granules into a vacuum oven, and performing vacuum drying at 110 ℃ for 9h to obtain the dried PET granules.
(3) And (3) reaction extrusion granulation: weighing 1kg of dried PET granules, 200g of dried surface-modified hollow floating beads, 1.2g of TGIC, 4.8g of MDI, 2g of antioxidant 1010 and 2g of TEPA, fully stirring and uniformly mixing to prepare a mixed material; and then putting the mixed material into a screw extruder for reaction extrusion and granulation, and adjusting the temperature of each area of the double screws as follows: 130 ℃ in the first zone, 150 ℃ in the second zone, 170 ℃ in the third zone, 210 ℃ in the fourth zone, 240 ℃ in the fifth zone, 250 ℃ in the sixth zone, 250 ℃ in the seventh zone, 260 ℃ in the eighth zone, 260 ℃ in the ninth zone, 255 ℃ in the machine head, 7Hz in the rotating frequency of the feeding machine of the double-screw extruder and 7Hz in the rotating frequency of the main machine, and finally the polyethylene terephthalate with low fluidity and easy processing and lightening property is prepared.
(example 3)
A preparation method of polyethylene terephthalate with low fluidity and easy processing and weight reduction comprises the following steps:
(1) carrying out surface modification on the hollow floating bead by using a silane coupling agent: firstly, the particle size is 1-250 μm, and the volume weight is 250-450 kg/m3Weighing a silane coupling agent with the mass being 4% of that of the hollow floating beads in a beaker, preparing the silane coupling agent into an ethanol water solution with the concentration of 5%, adjusting the mass ratio of ethanol to water to be 7:1, adjusting the pH value to 4 by using acetic acid, stirring for 1.5h at room temperature to fully hydrolyze the silane coupling agent, then putting the weighed hollow floating beads, carrying out ultrasonic treatment for 1.5h to uniformly mix the hollow floating beads, placing the mixture in a 60 ℃ water bath kettle, carrying out mechanical stirring reaction for 3h, then taking out the mixture, cooling the mixture to room temperature, carrying out repeated suction filtration and washing on the surface-modified hollow floating bead solution, drying the material after washing, then slightly grinding the dried material, and screening to prepare the surface-modified hollow floating beads with the particle size of 80 meshes for later use.
(2) And (3) drying treatment: drying the surface-modified hollow floating bead in the step (1) in a drying oven at 110 ℃ for 3h to obtain a dried surface-modified hollow floating bead; and (3) drying the PET granules with the melting point of 250-255 ℃ and the initial intrinsic viscosity of 0.7-0.8 dL/g in a forced air oven at 125 ℃ for 10h, transferring the PET granules into a vacuum oven, and performing vacuum drying at 125 ℃ for 10h to obtain the dried PET granules.
(3) And (3) reaction extrusion granulation: weighing 2kg of dried PET granules, 600g of dried surface-modified hollow floating beads, 8g of TGIC, 12g of MDI, 6g of antioxidant CA and 6g of TMP, fully stirring and uniformly mixing to prepare a mixed material; and then putting the mixed material into a screw extruder for reaction extrusion and granulation, and adjusting the temperature of each area of the double screws as follows: 140 ℃ in the first zone, 160 ℃ in the second zone, 180 ℃ in the third zone, 220 ℃ in the fourth zone, 250 ℃ in the fifth zone, 260 ℃ in the sixth zone, 260 ℃ in the seventh zone, 270 ℃ in the eighth zone, 270 ℃ in the ninth zone, 265 ℃ in the head, 9Hz in the rotating frequency of the feeding machine of the double-screw extruder and 9Hz in the rotating frequency of the main machine, and finally the polyethylene glycol terephthalate with low fluidity and easy processing and lightening is prepared.
(example 4)
A preparation method of polyethylene terephthalate with low fluidity and easy processing and weight reduction comprises the following steps:
(1) carrying out surface modification on the hollow floating bead by using a silane coupling agent: firstly, the particle size is 1-250 μm, and the volume weight is 250-450 kg/m3Weighing a silane coupling agent with the mass being 6% of that of the hollow floating beads in a beaker, preparing the silane coupling agent into an ethanol water solution with the concentration of 5%, adjusting the pH value to 5 by using acetic acid, stirring the mixture at room temperature for 2 hours to fully hydrolyze the silane coupling agent, adding the weighed hollow floating beads, carrying out ultrasonic treatment for 2 hours to uniformly mix the hollow floating beads, placing the mixture in a 70 ℃ water bath kettle to mechanically stir the mixture for reaction for 4 hours, taking the mixture out and cooling the mixture to room temperature, repeatedly carrying out suction filtration and washing on the surface-modified hollow floating bead solution, drying the material after washing, slightly grinding the dried material, and screening the surface-modified hollow floating beads with the particle size of 90 meshes for later use.
(2) And (3) drying treatment: drying the surface-modified hollow floating bead in the step (1) in an oven at 120 ℃ for 4h to obtain a dried surface-modified hollow floating bead; and (3) drying the PET granules with the melting point of 250-255 ℃ and the initial intrinsic viscosity of 0.7-0.8 dL/g in a forced air oven at 130 ℃ for 11h, transferring the PET granules into a vacuum oven, and performing vacuum drying at 130 ℃ for 11h to obtain the dried PET granules.
(3) And (3) reaction extrusion granulation: weighing 3kg of dried PET granules, 1200g of dried surface-modified hollow floating beads, 21.6g of TGIC, 14.4g of MDI, 12g of antioxidant 1010 and 12g of TEPA, fully stirring and uniformly mixing to obtain a mixed material; and then putting the mixed material into a screw extruder for reaction extrusion and granulation, and adjusting the temperature of each area of the double screws as follows: the first zone is 150 ℃, the second zone is 170 ℃, the third zone is 190 ℃, the fourth zone is 230 ℃, the fifth zone is 255 ℃, the sixth zone is 270 ℃, the seventh zone is 270 ℃, the eighth zone is 270 ℃, the ninth zone is 270 ℃, the machine head is 265 ℃, the rotating frequency of a double-screw extruder feeder is 11Hz, and the rotating frequency of a main machine is 11Hz, so that the polyethylene terephthalate with low fluidity and easy processing and lightening is finally prepared.
(example 5)
A preparation method of polyethylene terephthalate with low fluidity and easy processing and weight reduction comprises the following steps:
(1) carrying out surface modification on the hollow floating bead by using a silane coupling agent: firstly, the particle size is 1-250 μm, and the volume weight is 250-450 kg/m3Weighing a silane coupling agent with the mass being 8% of that of the hollow floating beads in a beaker, preparing the silane coupling agent into an ethanol water solution with the concentration of 7%, adjusting the pH value of the silane coupling agent to 6 by using acetic acid with the mass ratio of the ethanol to the water being 9:1, stirring the silane coupling agent for 3 hours at room temperature to fully hydrolyze the silane coupling agent, then putting the weighed hollow floating beads into the beaker, carrying out ultrasonic treatment for 3 hours to uniformly mix the hollow floating beads, then putting the hollow floating beads into a water bath kettle at 80 ℃ to mechanically stir the mixture for reaction for 5 hours, then taking the mixture out and cooling the mixture to the room temperature, then repeatedly carrying out suction filtration and washing on the surface-modified hollow floating bead solution, drying the material after washing, then slightly grinding and screening the dried material to prepare the surface-modified hollow floating beads with the particle size of 80 meshes for later use.
(2) And (3) drying treatment: drying the surface-modified hollow floating bead in the step (1) in an oven at 130 ℃ for 4h to obtain a dried surface-modified hollow floating bead; and (3) drying the PET granules with the melting point of 250-255 ℃ and the initial intrinsic viscosity of 0.7-0.8 dL/g in a forced air oven at 140 ℃ for 12h, transferring the PET granules into a vacuum oven, and performing vacuum drying at 130 ℃ for 4h to obtain the dried PET granules.
(3) And (3) reaction extrusion granulation: weighing 2kg of dried PET granules, 1000g of dried surface-modified hollow floating beads, 28.8g of GDE, 7.2g of MDI, 10g of antioxidant 1010 and 10g of TPP, fully stirring and uniformly mixing to obtain a mixed material; and then putting the mixed material into a screw extruder for reaction extrusion and granulation, and adjusting the temperature of each area of the double screws as follows: the first zone is 150 ℃, the second zone is 160 ℃, the third zone is 170 ℃, the fourth zone is 230 ℃, the fifth zone is 250 ℃, the sixth zone is 275 ℃, the seventh zone is 275 ℃, the eighth zone is 275 ℃, the ninth zone is 275 ℃, the machine head is 270 ℃, the rotating frequency of a double-screw extruder feeder is 13Hz, and the rotating frequency of a main machine is 13Hz, so that the polyethylene terephthalate with low fluidity and easy processing and lightening is finally prepared.
(example 6)
A preparation method of polyethylene terephthalate with low fluidity and easy processing and weight reduction comprises the following steps:
(1) carrying out surface modification on the hollow floating bead by using a silane coupling agent: firstly, the particle size is 1-250 μm, and the volume weight is 250-450 kg/m3Weighing a silane coupling agent with the mass being 10% of that of the hollow floating beads in a beaker, preparing the silane coupling agent into an ethanol water solution with the concentration of 8%, adjusting the pH value of the silane coupling agent to 7 by using acetic acid with the mass ratio of the ethanol to the water being 10:1, stirring the mixture at room temperature for 4 hours to fully hydrolyze the silane coupling agent, adding the weighed hollow floating beads, carrying out ultrasonic treatment for 3 hours to uniformly mix the hollow floating beads, placing the mixture in a 90 ℃ water bath kettle for mechanical stirring reaction for 6 hours, then taking out the mixture and cooling the mixture to the room temperature, then repeatedly carrying out suction filtration and washing on the surface-modified hollow floating bead solution, drying the material after washing, then slightly grinding and screening the dried material to prepare the surface-modified hollow floating beads with the particle size of 100 meshes for later use.
(2) And (3) drying treatment: drying the surface-modified hollow floating bead in the step (1) in an oven at 150 ℃ for 5 hours to obtain a dried surface-modified hollow floating bead; and (3) drying the PET granules with the melting point of 250-255 ℃ and the initial intrinsic viscosity of 0.7-0.8 dL/g in a forced air oven at 150 ℃ for 14h, transferring the PET granules into a vacuum oven, and performing vacuum drying at 150 ℃ for 5h to obtain the dried PET granules.
(3) And (3) reaction extrusion granulation: weighing 4kg of dried PET granules, 2000g of dried surface-modified hollow floating beads, 72g of HDE, 8g of HDI, 24g of antioxidant CA and 24g of TEPA, fully stirring and uniformly mixing to obtain a mixed material; and then putting the mixed material into a screw extruder for reaction extrusion and granulation, and adjusting the temperature of each area of the double screws as follows: the first zone is 180 ℃, the second zone is 180 ℃, the third zone is 210 ℃, the fourth zone is 260 ℃, the fifth zone is 260 ℃, the sixth zone is 280 ℃, the seventh zone is 280 ℃, the eighth zone is 280 ℃, the ninth zone is 280 ℃, the head is 280 ℃, the rotation frequency of a double-screw extruder feeder is 20Hz, and the rotation frequency of a main machine is 20Hz, so that the polyethylene terephthalate with low fluidity and easy processing and lightening is finally prepared.
Comparative example 1
A preparation method of PET resin comprises the following steps:
the PET pellets were first dried in a forced air oven at 130 ℃ for 10h, then transferred to a vacuum oven and dried in vacuum at 130 ℃ for 10h to give dried PET pellets.
Comparative example 2
A preparation method of polyethylene terephthalate with low fluidity and easy processing and weight reduction comprises the following steps:
(1) carrying out surface modification on the hollow floating bead by using a silane coupling agent: firstly, the particle size is 1-250 μm, and the volume weight is 250-450 kg/m3Weighing a silane coupling agent with the mass being 2% of that of the hollow floating beads in a beaker, preparing the silane coupling agent into an ethanol water solution with the concentration of 5%, adjusting the mass ratio of ethanol to water to be 6:1, adjusting the pH value to 3 by using acetic acid, stirring for 1 hour at room temperature to fully hydrolyze the silane coupling agent, adding the weighed hollow floating beads, carrying out ultrasonic treatment for 1 hour to uniformly mix the hollow floating beads, placing the mixture in a 50 ℃ water bath kettle for mechanical stirring reaction for 2 hours, taking out the mixture, cooling to room temperature, repeatedly carrying out suction filtration and washing on the surface-modified hollow floating bead solution, drying the material after washing, slightly grinding the dried material, and screening to prepare the surface-modified hollow floating beads with the particle size of 60 meshes for later use.
(2) And (3) drying treatment: drying the surface-modified hollow floating bead in the step (1) in a drying oven at 100 ℃ for 2h to obtain a dried surface-modified hollow floating bead; and (3) drying the PET granules with the melting point of 250-255 ℃ and the initial intrinsic viscosity of 0.7-0.8 dL/g in a forced air oven at 110 ℃ for 9h, transferring the PET granules into a vacuum oven, and performing vacuum drying at 110 ℃ for 9h to obtain the dried PET granules.
(3) And (3) reaction extrusion granulation: weighing 1kg of dried PET granules, 200g of dried surface-modified hollow floating beads, 6g of TGIC, 2g of antioxidant 1010 and 2g of TEPA, fully stirring and uniformly mixing to obtain a mixed material; and then putting the mixed material into a screw extruder for reaction extrusion and granulation, and adjusting the temperature of each area of the double screws as follows: 130 ℃ in the first zone, 150 ℃ in the second zone, 170 ℃ in the third zone, 210 ℃ in the fourth zone, 240 ℃ in the fifth zone, 250 ℃ in the sixth zone, 250 ℃ in the seventh zone, 260 ℃ in the eighth zone, 260 ℃ in the ninth zone, 255 ℃ in the machine head, 7Hz in the rotating frequency of the feeding machine of the double-screw extruder and 7Hz in the rotating frequency of the main machine, and finally the polyethylene terephthalate with low fluidity and easy processing and lightening property is prepared.
(comparative example 3)
A preparation method of low-fluidity and easy-to-process polyethylene terephthalate comprises the following steps:
(1) and (3) drying treatment: and (3) drying the PET granules with the melting point of 250-255 ℃ and the initial intrinsic viscosity of 0.7-0.8 dL/g in a forced air oven at 110 ℃ for 9h, transferring the PET granules into a vacuum oven, and performing vacuum drying at 110 ℃ for 9h to obtain the dried PET granules.
(2) And (3) reaction extrusion granulation: weighing 1kg of dried PET granules 1.2g of TGIC, 4.8g of MDI, 2g of antioxidant 1010 and 2g of TEPA, fully stirring and uniformly mixing to prepare a mixed material; and then putting the mixed material into a screw extruder for reaction extrusion and granulation, and adjusting the temperature of each area of the double screws as follows: 130 ℃ in the first zone, 150 ℃ in the second zone, 170 ℃ in the third zone, 210 ℃ in the fourth zone, 240 ℃ in the fifth zone, 250 ℃ in the sixth zone, 250 ℃ in the seventh zone, 260 ℃ in the eighth zone, 260 ℃ in the ninth zone, 255 ℃ in the head, 7Hz in the rotating frequency of the feeding machine of the double-screw extruder and 7Hz in the rotating frequency of the main machine, and finally the polyethylene glycol terephthalate with low fluidity and easy processing is prepared.
(comparative example 4)
A preparation method of polyethylene terephthalate with low fluidity and easy processing and weight reduction comprises the following steps:
(1) and (3) drying treatment: drying PET granules with the melting point of 250-255 ℃ and the initial intrinsic viscosity of 0.7-0.8 dL/g for 9h at 110 ℃ in a forced air oven, transferring the PET granules into a vacuum oven, and performing vacuum drying for 9h at 110 ℃ to obtain dried PET granules; the unmodified particle size is 1-250 μm, and the volume weight is 250-450 kg/m3The hollow floating beads are washed for at least 3 times in distilled water and dried in an oven at 90 ℃ for 3 hours to obtain dry unmodified hollow floating beads.
(2) And (3) reaction extrusion granulation: weighing 1kg of dried PET granules, 200g of dried unmodified hollow floating beads, 1.2g of TGIC, 4.8g of MDI, 2g of antioxidant 1010 and 2g of TEPA, fully stirring and uniformly mixing to prepare a mixed material; and then putting the mixed material into a screw extruder for reaction extrusion and granulation, and adjusting the temperature of each area of the double screws as follows: 130 ℃ in the first zone, 150 ℃ in the second zone, 170 ℃ in the third zone, 210 ℃ in the fourth zone, 240 ℃ in the fifth zone, 250 ℃ in the sixth zone, 250 ℃ in the seventh zone, 260 ℃ in the eighth zone, 260 ℃ in the ninth zone, 255 ℃ in the machine head, 7Hz in the rotating frequency of the feeding machine of the double-screw extruder and 7Hz in the rotating frequency of the main machine, and finally the polyethylene terephthalate with low fluidity and easy processing and lightening property is prepared.
(Effect embodiment 1)
The low-fluidity and easy-to-process and lightweight polyethylene terephthalate samples prepared in the step (3) of examples 1 to 6 were compared with the PET resin sample of comparative example 1 and the low-fluidity and easy-to-process and lightweight polyethylene terephthalate sample prepared in comparative example 2 in terms of performance, and the intrinsic viscosity and the melt index were measured, respectively. The intrinsic viscosity is measured by adopting an Ubbelohde viscometer, a mixed solution of phenol and 1,1, 2-trichloroethane in a mass ratio of (2:3) is used as a solvent, 0.3 +/-0.01 g of a test sample is weighed, the test sample and the prepared solvent are magnetically stirred and dissolved in an oil bath at 100 ℃ for 1 hour, a 50ml volumetric flask is used for metering the volume, and the solution is taken to be measured by the Ubbelohde viscometer with the diameter of a capillary tube of 0.5-0.6 mm at the temperature of 25 seconds and 0.1 ℃. The melt index is tested by using a melt flow rate meter (MTM 1000-A1 model) of Shenzhen Sansi longitudinal and transverse science and technology Limited company, the temperature of the melt flow rate meter is set to 260 ℃ before testing, 3-5 g of sample is placed after the temperature is stable, the sample is rapidly compacted by a material pressing rod, the influence of air is eliminated, the test is started after the sample is melted for 4min, and 2160g of material pressing code removing is selected (T-shaped code removing and material rod component). The test results are shown in Table 1.
TABLE 1 intrinsic viscosity and melt index of PET resins obtained by different processes
As can be seen from Table 1, the low-fluidity and lightweight polyethylene terephthalate resin prepared by the invention has the intrinsic viscosity increased from 0.70dL/g to 0.84dL/g, 0.85dL/g, 0.89dL/g, 1.31dL/g, 1.10dL/g and 0.92dL/g respectively, and the melt index decreased from 80g/10min to 35.3g/10min, 34.3g/10min, 31g/10min, 14.7g/10min, 24.8g/10min and 25.5g/10min respectively. The intrinsic viscosity is obviously improved, the melt strength is increased, the degradation of molecular chains is compensated, and the processing performance is improved.
(Effect embodiment 2)
The polyethylene terephthalate resin with low fluidity and easy processing and weight reduction prepared in the step (3) in the embodiments 1 to 6 and the polyethylene terephthalate resin prepared in the comparative examples 1,2, 3 and 4 are injected into national standard sample bars, each set of sample bar is not less than five, and each mechanical property test and apparent density test are carried out after the sample bars are placed for 24 hours. The tensile property test is carried out on a WDT10 type tensile testing machine of Keqianli experimental apparatus Limited in Shenzhen according to the standard of GB/T1040-2, the testing speed is 50mm/min, and the distance between clamps is 50 mm; the bending performance test is carried out on a WDT10 type three-point bending tester of Kelly strong experimental instrument Limited in Shenzhen according to the standard of GB/T1040-2, and the test speed is 2 mm/min; the notched impact strength was tested on an XJU-22 type impact tester, Dahua tester, Inc., of Chengde, according to the standard of the national Standard GB/T1843-2008, with a bar size of 80 mm. times.10 mm. times.4 mm, a V-shaped notch, and a notch depth of 2 mm. The apparent density is one of the important parameters characterizing the foamed material. The measurement is carried out by a density balance, the measurement principle is that M of a test sample is passed1And M2Calculated from the formula (1-1) derived from Archimedes drainage method.
In the formula, rho-apparent density, g/cm3；
M1-mass of the sample in air, g;
M2mass of the sample in water, g.
The test results are shown in Table 2
TABLE 2 mechanical Properties and apparent Density of PET resins obtained by different methods
As is clear from Table 2, in examples 1 to 6, the apparent density of the polyethylene terephthalate obtained by adding the floating beads was actually lowered to a different degree from that of comparative example 1, comparative example 2 and comparative example 3, and the lowest apparent density was 0.65g/cm3(ii) a Although the mechanical properties are improved to different degrees compared with comparative example 1, the mechanical properties of the examples show a tendency of fluctuation with the change of the addition amount of the floating beads, and the difference exists between the combination of the chain extenders and the combination of the chain extenders. Wherein example 4 has a tensile strength of 76.5MPa, a flexural strength of 75.8MPa, and an impact strength of 6.1KJ/m2The improvement is respectively 52.1 percent, 27.8 percent and 22 percent compared with the pure PET granules.
In examples 1 to 6 and comparative example 4, it was found that although the apparent density was decreased, the former was improved in mechanical properties compared to the latter, which indicates that the modified floating beads could be dispersed in the resin matrix better, i.e., the compatibility was good. Wherein the notched impact strength of example 4 was 6.1KJ/m2Compared with comparative example 4, the improvement is 69.4%, and it can be known that whether the microbeads are subjected to surface modification treatment has certain influence on the mechanical properties of the polyethylene terephthalate which has low fluidity and is easy to process and lighten, wherein the influence on the notch impact strength is most obvious.
Therefore, the apparent density of the polyethylene terephthalate prepared after chain extension modification and weight reduction is greatly reduced, and the mechanical property is reduced to a certain extent but is still higher than that of pure PET.
Claims (9)
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