CN105273368A - Foamable PET resin, preparation method and uses thereof - Google Patents
Foamable PET resin, preparation method and uses thereof Download PDFInfo
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Abstract
The present invention discloses a foamable PET resin, a preparation method and uses thereof. The preparation method comprises: (1) uniformly mixing raw material components, wherein the raw material components comprise 985-995 parts of physically recycled PET bottle flakes, 1-9 parts of a chain extender, 1-3 parts of an antioxidant, and 1-3 parts of a thermal stabilizer, and a three-functional-group chain extension monomer and a multi-functional-group chain extension monomer having a functional group number of 4-6 are compounded according to a mass ratio of 1:3-5:1 to prepare the chain extender; (2) carrying out melt extrusion granulation; and (3) carrying out solid phase condensation polymerization on the obtained material for 1-5 h at a temperature of 210-230 DEG C under a vacuum degree of 5-100 Pa so as to obtain the foamable PET resin. According to the present invention, the foamed PET resin has characteristics of high molecular weight, wide molecular weight distribution, high melt strength, physically recycled PET degrading use changing, low raw material cost, and simple preparation process; and with the combination of the chain extender, the reaction extrusion and the solid phase condensation polymerization are combined, such that the reaction period is shortened, and the industrial production is easily achieved.
Description
Technical field
The present invention relates to a kind of polyester foam materials, particularly relating to one can foaming PET resin and its production and use.
Background technology
Polyethylene terephthalate (PET) is maximum, the cheapest kind of price of output in thermoplastic polyester, there is excellent physics, chemistry and mechanics mechanical property, be widely used in the large field of synthon, biaxially oriented film and polyester bottles three, also show wide application prospect in foam materials field in recent years.PET polyester foam materials has that quality is light, specific tenacity is large, rigidity is large, electrical insulating property is good and the advantage such as sound deadener/insulator, can be applicable to the fields such as food product pack, material of construction, wire insulation, microwave container, refrigerator inner panel, sports equipment, automobile, space flight.Current China PET polyester ultimate production is greatly about 1 ~ 3,000 ten thousand ton/year.Because PET polyester product mostly is disposable products or easily-consumed products, produce and in use procedure with a large amount of wastes, and PET waste can not spontaneous degradation, easily causes serious environmental pollution and the wasting of resources.Therefore the recovery of PET waste and regeneration have important practical significance.
PET Polyester waste recovery method mainly contains chemical recovery and physiochemical mutagens.Chemical recovery is the method by sugar solution, alcoholysis and hydrolysis, PET polyester is decomposed into oligopolymer and monomer, then regroups as PET polyester.Although can realize the complete cycling and reutilization of PET Polyester waste, cost is comparatively large, cannot large-scale promotion.Physiochemical mutagens method is carried out reproducing grain by waste PET polyester after classification, fragmentation, washing and drying treatment, is supplied to the starting material of fiber factory as producd fibers.But along with processing the increasing of number of times, the limiting viscosity of PET polyester, molecular weight distribution and foreign matter content all can constantly change, and cause physiochemical mutagens to utilize number of times limited.Therefore simple physiochemical mutagens method is actually a kind of Application way reclaimed by unidirectional for PET polyester degradation, i.e. bottle sheet-fiber, fiber-dead meal, and the method for there is no realizes complete closed loop and recycles.
Conventional PET polyester is due in the continuous foamed process of industrial melting, and melt strength, melt viscosity and extensional viscosity are less, and melt rheological property can be poor, cannot support growth and the sizing of abscess; And PET polyester is at high temperature easily hydrolyzed, pyrolysis and thermooxidative degradation, causes can not get good abscess in foaming process.And the PET polyester that physiochemical mutagens method obtains is because limiting viscosity is low, foreign matter content is high, increase the technical difficulty preparing foaming PET resin further.Therefore, for overcoming the defect of physiochemical mutagens PET polyester, modification must be carried out to Pillar recovery, improving the molecular weight of PET polyester, widening molecular weight distribution, increase long chain branching degree, to be obtained the foaming PET resin with good foam structure by melt foaming.
Existing PET polyester reclaims modification and mainly adopts chemical thickening method, generally realizes with the processing method of reactive extrursion.Usually adopt chemical chainextender and recycled PET exposed terminated groups to carry out chain extending reaction in the molten state, increase PET molecular weight, thus improve the limiting viscosity of PET.GerogeP has prepared 2,2 '-(Isosorbide-5-Nitrae-phenylene) two (bisoxazoline), and make chainextender with it, modification is carried out to recycled PET beverage bottle.The viscosity of Pillar recovery PET is elevated to the 0.85dL/g after thickening by the 0.69dL/g before thickening, reaches good Efficient Adhesive Promotion [Journalofappliedpolymerscience, 2000,77 (6): 2206-2211].Domestic relevant report is also a lot, Cai Changgeng etc. are with 2,2-two (2-bisoxazoline) (BOZ) carries out modification with Tetra hydro Phthalic anhydride (PA) coupling to the Pillar recovery PET that limiting viscosity is 0.411dL/g, when the limiting viscosity of alone BOZ chain extension Pillar recovery PET increases about 10%, reach 0.457dL/g, and limiting viscosity reaches 0.695dL/g after BOZ and PA coupling, improve nearly 75%.Therefore, the method for employing chainextender coupling achieves the object [plastics, 2005,34 (2): 63-66] to Pillar recovery PET modification thickening preferably.By reactive extrursion, the limiting viscosity of PET increases to some extent, can reach the requirement of industrial processes.But because the melt strength of PET can not be brought up to the intensity needed for foaming by reactive extrursion, so modified PET is not still suitable for foaming, do not reach the requirement of foaming.The toughener such as He Jianxin, toughner, fire retardant, clay, nucleator, oxidation inhibitor proportioning, extruded by twin screw extruder, obtained high performance, high strength, energy-conserving and environment-protective, PET material [Chinese invention patent, CN201010196709.5] that flame retardant resistance is high.And by modifications such as toughner, although the physical strength of energy REINFORCED PET, molecular structure is also not suitable for foaming.Therefore, as how a kind of low cost, mode capable of being industrialized, utilize recycled PET polyester for raw material, preparation can foaming PET resin, is that this area scientific research personnel has technical problem to be solved.
Summary of the invention
It is low that technical problem to be solved by this invention is to overcome existing physiochemical mutagens PET molecular weight of polyesters, melt strength is poor, in reactive extrursion, be difficult to the defect that normal foaming and simple toughner chemical modification PET molecular structure are not suitable for foaming, providing one can foaming PET resin and its production and use.Of the present invention can foaming PET resin with physiochemical mutagens PET bottle sheet for raw material, with low cost, preparation process is simple, by chainextender coupling, adopt reactive extrursion and solid phase polycondensation two processes, effectively improve the melt strength of PET, shorten the reaction time of conventional solid polycondensation, be more conducive to suitability for industrialized production.And the present invention prepare can foaming PET molecular resin amount large, molecular weight distribution is wide, melt strength is high, the degradation not only changing physiochemical mutagens PET uses, and the introduction of solid phase polycondensation process, decrease micromolecular existence, reduce side reaction, make modified PET have good foam performance, can be used for preparation PET foam article.
The invention provides a kind of can the preparation method of foaming PET resin, it comprises the steps:
(1) by feed composition mixing and stirring; Described feed composition comprises physiochemical mutagens PET bottle sheet 985 ~ 995 parts, chainextender 1 ~ 9 part, 1 ~ 3 part, oxidation inhibitor, thermo-stabilizer 1 ~ 3 part; Described chainextender by trifunctional extend monomer and polyfunctional group extend monomer in mass ratio 1:3 ~ 5:1 carry out composite, described polyfunctional group extend monomer be functional group number 4 ~ 6 extend monomer;
(2) by material melts extruding pelletization that step (1) mixes;
(3) material step (2) granulation obtained is in 210 ~ 230 DEG C, solid phase polycondensation 1 ~ 5h under 5 ~ 100Pa vacuum tightness, and obtaining can foaming PET resin.
In step (1), described physiochemical mutagens PET bottle sheet is the PET bottle sheet that this area Typical physical absorption method obtains; The fusing point of described physiochemical mutagens PET bottle sheet is preferably 252 ~ 256 DEG C, and initial intrinsic viscosity is preferably 0.6 ~ 0.7dL/g.
In step (1), described physiochemical mutagens PET bottle sheet is preferably through super-dry pre-treatment; Described dry pre-treatment preferably adopts following step: first 100 ~ 120 DEG C of drying 10 ~ 15h in convection oven, are then transferred in vacuum drying oven, 120 ~ 150 DEG C of vacuum-drying 10 ~ 15h.
In step (1), described chainextender is the chainextender of this area routine; Described trifunctional chainextender is preferably triglycidyl isocyanurate (TGIC), and described polyfunctional group extend monomer is preferably four-functional group chainextender pyromellitic dianhydride (PMDA) and/or six functional groups chainextender ADR4370.
In step (1), described oxidation inhibitor is the oxidation inhibitor of this area routine, is preferably antioxidant 1010 and/or irgasfos 168; The fusing point of described antioxidant 1010 is 110.0 ~ 125.0 DEG C, and density is 1.15g/cm
3, the fusing point of described irgasfos 168 is 182 ~ 186 DEG C, and density is 1.03g/cm
3.
In step (1), described thermo-stabilizer is the thermo-stabilizer of this area routine, is preferably triphenyl phosphite (TPP) and/or triethylene thiophosphoramide (TEPA); The fusing point of described thermo-stabilizer TPP is 22 ~ 24 DEG C, relative molecular weight is 310.29, density is 1.184g/cm
3, the fusing point of described thermo-stabilizer TEPA is-40 DEG C, density is 0.998g/cm
3.
In step (2), the described granulation that melt extrudes is this area routine operation, preferably adopts twin screw extruder to carry out; One district's temperature of described twin screw extruder is preferably 255 ~ 275 DEG C, two district's temperature are preferably 255 ~ 275 DEG C, three district's temperature are preferably 260 ~ 280 DEG C, four district's temperature are preferably 260 ~ 280 DEG C, five district's temperature are preferably 255 ~ 275 DEG C, six district's temperature are preferably 255 ~ 275 DEG C; Described twin screw extruder feeding machine feeding frequency is preferably 10 ~ 20Hz, and main frame rotational frequency is preferably 10 ~ 20Hz.
In step (3), before carrying out described solid phase polycondensation, described material is preferably through drying treatment; Described drying treatment preferably adopts following step: first 100 ~ 120 DEG C of drying 10 ~ 15h in convection oven, are then transferred in vacuum drying oven, 100 ~ 120 DEG C of vacuum drying 10 ~ 15h.
Present invention also offers a kind of by aforesaid method obtain can foaming PET resin.
Of the present invention can have long chain branched by foaming PET resin, and molecular weight is large, molecular weight distribution is wide, and melt strength is high.Of the present invention can foaming PET resin properties viscosity >=0.8dL/g, melting index≤25g/10min.
Present invention also offers a kind of by aforesaid method obtain can the purposes of foaming PET resin in PET foam article.
According to this area general knowledge, of the present inventionly can the working method of this area routine be adopted to foam by foaming PET resin, such as, adopt melting batch-foamed method and/or micropore injection moulding shaping foam method.
On the basis meeting this area general knowledge, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material are all commercially.
Positive progressive effect of the present invention is:
1, the present invention by physiochemical mutagens PET bottle sheet with coupling chainextender, oxidation inhibitor, the modification of thermo-stabilizer blending extrusion in conjunction with process for solid state polycondensation, the degradation changing physiochemical mutagens PET uses, impart the foam performance that PET is good, can be used for preparation PET foam article.
2, the present invention with physiochemical mutagens PET bottle sheet for raw material, can foaming PET resin by twin screw reactive extrursion and process for solid state polycondensation preparation, with low cost, low for equipment requirements, preparation process is simple, is conducive to suitability for industrialized production.
What 3, prepared by the present invention can foaming PET resin, and extrude more merely modification method, melt strength is higher; More simple process for solid state polycondensation, the polycondensation time is shorter, has greatly reduced the number of the operational cycle.
Accompanying drawing explanation
Fig. 1 is the complex viscosity figure of PET resin prepared by embodiment 1 ~ 2 and comparative example;
Fig. 2 is the springform spirogram of PET resin prepared by embodiment 1 ~ 2 and comparative example;
Fig. 3 is the viscous modulus figure of PET resin prepared by embodiment 1 ~ 2 and comparative example;
Fig. 4 be embodiment 2 prepare can foaming PET resin (c, and the PET bottle sheet base-material (a of comparative example d), b) the SEM photo under different blowing temperature after foaming: (a) 265 DEG C, (b) 275 DEG C, (c) 265 DEG C, (d) 275 DEG C;
Fig. 5 be embodiment 1 prepare can the SEM photo of foaming PET resin under 265 DEG C of blowing temperatures.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or selects according to catalogue.
In following embodiment:
Described pyromellitic dianhydride (PMDA) is provided by Shanghai Ao highland barley Industrial Co., Ltd., commercially available; Described six functional groups chainextender (ADR4370) completes bio tech ltd by citizen of Guangzhou City to be provided, commercially available.Described triglycidyl isocyanurate (TGIC), antioxidant 1010, irgasfos 168, triphenyl phosphite (TPP) and triethylene thiophosphoramide (TEPA) provide by Chemical Reagent Co., Ltd., Sinopharm Group, commercially available.
In following embodiment, the fusing point of physiochemical mutagens PET bottle sheet is 252 ~ 256 DEG C, and initial intrinsic viscosity is 0.6 ~ 0.7dL/g.
Embodiment 1
Can the preparation method of foaming PET resin, it comprises the steps:
1, by discarded PET bottle sheet 100 DEG C of dry 13h in convection oven, transfer to 135 DEG C of vacuum-drying 14h in vacuum drying oven, obtain physiochemical mutagens PET bottle sheet;
2, take 4kg physiochemical mutagens PET bottle sheet, 12gTGIC, 4gPMDA, 4g antioxidant 1010,4gTPP, mix rear input twin screw extruder extruding pelletization; Control twin screw extruder each section of temperature to exist: 260 DEG C, a district, 260 DEG C, 2nd district, 265 DEG C, 3rd district, 265 DEG C, 4th district, 260 DEG C, 5th district, 260 DEG C, 6th district; Twin screw extruder feeding machine rotational frequency 15hz, main frame rotational frequency 13.5hz;
3, grain will be extruded after 120 DEG C of dry 12h, take out and carry out solid phase polycondensation, wherein temperature of reaction 220 DEG C, vacuum tightness 20Pa, polycondensation time 2h in convection oven and vacuum drying oven respectively.
Embodiment 2
Can the preparation method of foaming PET resin, it comprises the steps:
1, by discarded PET bottle sheet 110 DEG C of dry 12h in convection oven, transfer to 140 DEG C of dry 12h in vacuum drying oven, obtain physiochemical mutagens PET bottle sheet;
2, take 2kg physiochemical mutagens PET bottle sheet, 8gTGIC, 2gPMDA, 2g antioxidant 1010,2gTPP, mix rear input twin screw extruder extruding pelletization; Control twin screw extruder each section of temperature to exist: 255 DEG C, a district, 255 DEG C, 2nd district, 255 DEG C, 3rd district, 265 DEG C, 4th district, 265 DEG C, 5th district, 265 DEG C, 6th district; Twin screw extruder feeding machine rotational frequency 15hz, main frame rotational frequency 13.5hz;
3, grain will be extruded after 100 DEG C of dry 15h, take out and carry out solid phase polycondensation, wherein temperature of reaction 220 DEG C, vacuum tightness 10Pa, polycondensation time 4h in convection oven and vacuum drying oven respectively.
Embodiment 3
Can the preparation method of foaming PET resin, it comprises the steps:
1, by discarded PET bottle sheet 110 DEG C of dry 12h in convection oven, transfer to 140 DEG C of dry 12h in vacuum drying oven, obtain physiochemical mutagens PET bottle sheet;
2, take 2kg physiochemical mutagens PET bottle sheet, 6gTGIC, 1gADR4730,2g irgasfos 168,3gTEPA, mix rear input twin screw extruder extruding pelletization; Control twin screw extruder each section of temperature to exist: 260 DEG C, a district, 265 DEG C, 2nd district, 270 DEG C, 3rd district, 265 DEG C, 4th district, 260 DEG C, 5th district, 260 DEG C, 6th district; Twin screw extruder feeding machine rotational frequency 15hz, main frame rotational frequency 13.5hz;
3, grain will be extruded after 110 DEG C of dry 12h, take out and carry out solid phase polycondensation, wherein temperature of reaction 210 DEG C, vacuum tightness 20Pa, polycondensation time 1h in convection oven and vacuum drying oven respectively.
Embodiment 4
Can the preparation method of foaming PET resin, it comprises the steps:
1, by discarded PET bottle sheet 110 DEG C of dry 12h in convection oven, transfer to 140 DEG C of dry 12h in vacuum drying oven, obtain physiochemical mutagens PET bottle sheet;
2, take 2kg physiochemical mutagens PET bottle sheet, 5gADR4370,2gTGIC, 6g antioxidant 1010,3gTEPA, mix rear input twin screw extruder extruding pelletization; Control twin screw extruder each section of temperature to exist: 265 DEG C, a district, 260 DEG C, 2nd district, 265 DEG C, 3rd district, 270 DEG C, 4th district, 265 DEG C, 5th district, 260 DEG C, 6th district; Twin screw extruder feeding machine rotational frequency 15hz, main frame rotational frequency 13.5hz;
3, grain will be extruded after 110 DEG C of dry 12h, take out and carry out solid phase polycondensation, wherein temperature of reaction 230 DEG C, vacuum tightness 20pa, polycondensation time 5h in convection oven and vacuum drying oven respectively.
Embodiment 5
Can the preparation method of foaming PET resin, it comprises the steps:
1, by discarded PET bottle sheet 110 DEG C of dry 12h in convection oven, transfer to 140 DEG C of dry 12h in vacuum drying oven, obtain physiochemical mutagens PET bottle sheet;
2, take 1kg physiochemical mutagens PET bottle sheet, 5gADR4370,4gTGIC, 1g antioxidant 1010,2gTEPA, mix rear input twin screw extruder extruding pelletization; Control twin screw extruder each section of temperature to exist: 265 DEG C, a district, 260 DEG C, 2nd district, 265 DEG C, 3rd district, 270 DEG C, 4th district, 265 DEG C, 5th district, 260 DEG C, 6th district; Twin screw extruder feeding machine rotational frequency 15hz, main frame rotational frequency 13.5hz;
3, grain will be extruded after 110 DEG C of dry 12h, take out and carry out solid phase polycondensation, wherein temperature of reaction 220 DEG C, vacuum tightness 20pa, polycondensation time 3h in convection oven and vacuum drying oven respectively.
Embodiment 6
Can the preparation method of foaming PET resin, it comprises the steps:
1, by discarded PET bottle sheet 110 DEG C of dry 12h in convection oven, transfer to 140 DEG C of dry 12h in vacuum drying oven, obtain physiochemical mutagens PET bottle sheet;
2, take 2kg physiochemical mutagens PET bottle sheet, 1gPMDA, 1gTGIC, 3g irgasfos 168,6gTPP, mix rear input twin screw extruder extruding pelletization; Control twin screw extruder each section of temperature to exist: 265 DEG C, a district, 265 DEG C, 2nd district, 270 DEG C, 3rd district, 270 DEG C, 4th district, 270 DEG C, 5th district, 265 DEG C, 6th district; Twin screw extruder feeding machine rotational frequency 15hz, main frame rotational frequency 15hz;
3, grain will be extruded after 110 DEG C of dry 12h, take out and carry out solid phase polycondensation, wherein temperature of reaction 210 DEG C, vacuum tightness 20pa, polycondensation time 4h in convection oven and vacuum drying oven respectively.
Comparative example
A preparation method for PET resin, it comprises the steps:
By discarded PET bottle sheet 110 DEG C of dry 12h in convection oven, transfer to 140 DEG C of dry 12h in vacuum drying oven, obtain physiochemical mutagens PET bottle sheet base-material.
Effect example 1
That embodiment 1 ~ 6 is prepared can the PET bottle sheet base-material of foaming PET resin and comparative example contrast, and distinguishes test characteristic viscosity and melting index.Described limiting viscosity adopts Ubbelohde viscometer to test, with mass ratio be the phenol of (50:50), tetrachloroethane mixed solution for solvent, the solution being made into 0.5% (wt.%) is the determination of ubbelohde viscometer of 0.7 ~ 0.8mm by capillary diameter at 25 ± 0.1 DEG C.Described melting index uses Shanghai Si Erda scientific instrument company limited RL-11B1 type Melt Flow Rate Measurer to adopt ASTM1238 standard to test, first melting means instrument temperature is set as 260 DEG C before test, stroke selects 3.175, after temperature-stable, put into the material of 3 ~ 5g, with compressing rod rapidly by material compacting, the impact of excluding air, after material melts 5min, start test, 2160g (T-shaped counterweight+material bar assembly) selected by binder counterweight.Test result is in table 1.
Table 1 different process is on the impact of PET limiting viscosity and melting index
As can be seen from Table 1, the PET resin that the present invention obtains, limiting viscosity brings up to 0.95,1.15,0.88,0.93,0.91 and 0.89dL/g respectively from 0.70dL/g, and melting index is reduced to 9.8,3.7,13.5,11.3,12.1 and 13.4g/10min from 34.The limiting viscosity of modified physiochemical mutagens PET significantly promotes, and melt strength increases.Wherein embodiment 2 material numerically all meets foaming necessary requirement in limiting viscosity and melting index, has very high melt strength.
Effect example 2
That embodiment 1 and 2 is prepared can the PET bottle sheet base-material of foaming PET resin and comparative example contrast, and measures rheological property respectively.Described rheological property adopts HAKKEMAR III plate rheometer to test, temperature 275 DEG C, test frequency 0.1 ~ 100rad/s.Test result is shown in Fig. 1 ~ 3, is evaluated the rheological property of material by complex viscosity, Young's modulus and viscous modulus.
As can be seen from Fig. 1 ~ 3, the PET resin complex viscosity that embodiment 2 obtains, Young's modulus, viscous modulus are all higher than the PET resin that embodiment 1 is obtained, and the PET resin complex viscosity of embodiment 2 has exceeded the order of magnitude of 10000 in low frequency range, shear shinning clearly, illustrates that modified effect is remarkable.
Effect example 3
That embodiment 1 ~ 2 is prepared can the PET bottle sheet base-material of foaming PET resin and comparative example contrast, and evaluates foaming effect by melting interrupter method and/or the micropore injection moulding method of forming.Described melt foaming process is blowing temperature 265 DEG C ~ 275 DEG C, and blow(ing) pressure 16MPa, saturation time 30min, carry out under quick pressure releasing.Described micropore injection moulding shaping foam process is at MuCell service platform, and melten gel amount 30 ~ 36mm, injection speed 60% ~ 90%, whipping agent supercritical nitrogen content 0.2% ~ 0.8%, melt temperature 265 ~ 280 DEG C, carries out at die temperature 30 ~ 90 DEG C.Described foaming effect adopts Jeol Ltd. JSM-6360LV type scanning electron microscopic observation cell morphology to analyze, first by sample cold quenching in liquid nitrogen before test, then on sample section metal spraying to strengthen its electroconductibility.The mean pore size of foamed sample is analyzed SEM photo by winroof software and obtains.
Fig. 4 is the SEM photo of the melting interrupter method foaming of comparative example and embodiment 2, wherein (a, b) be the SEM photo of PET bottle sheet base-material under 265 DEG C and 275 DEG C of blowing temperatures of comparative example, the SEM photo of PET resin under 265 DEG C and 275 DEG C of blowing temperatures that (c, d) is prepared for embodiment 2.Can find out, unmodified physiochemical mutagens PET bottle sheet is low due to melt strength, cannot support abscess growth wherein, thus cannot foaming.And the PET resin that embodiment 2 obtains has good foam performance, and abscess-size is comparatively even.This illustrates that the PET resin that embodiment 2 obtains has higher melt strength.
Fig. 5 be embodiment 1 prepare can foaming PET resin at 265 DEG C the micropore injection moulding method of forming foaming SEM photo.Can see, the PET foaming product that embodiment 1 obtains has more uniform foam structure, but cell density is less, and expansion ratio is lower.
Claims (10)
1. can the preparation method of foaming PET resin, it comprises the steps:
(1) by feed composition mixing and stirring; Described feed composition comprises physiochemical mutagens PET bottle sheet 985 ~ 995 parts, chainextender 1 ~ 9 part, 1 ~ 3 part, oxidation inhibitor, thermo-stabilizer 1 ~ 3 part; Described chainextender by trifunctional extend monomer and polyfunctional group extend monomer in mass ratio 1:3 ~ 5:1 carry out composite, described polyfunctional group extend monomer be functional group number 4 ~ 6 extend monomer;
(2) by material melts extruding pelletization that step (1) mixes;
(3) material step (2) granulation obtained is in 210 ~ 230 DEG C, solid phase polycondensation 1 ~ 5h under 5 ~ 100Pa vacuum tightness, and obtaining can foaming PET resin.
2. as claimed in claim 1 can the preparation method of foaming PET resin, it is characterized in that: described physiochemical mutagens PET bottle sheet fusing point is 252 ~ 256 DEG C, and initial intrinsic viscosity is 0.6 ~ 0.7dL/g.
3. as claimed in claim 1 can the preparation method of foaming PET resin, it is characterized in that: described physiochemical mutagens PET bottle sheet is through super-dry pre-treatment; Described dry pre-treatment adopts following step: first 100 ~ 120 DEG C of drying 10 ~ 15h in convection oven, are then transferred in vacuum drying oven, 120 ~ 150 DEG C of vacuum-drying 10 ~ 15h.
4. as claimed in claim 1 can the preparation method of foaming PET resin, it is characterized in that: described trifunctional chainextender is triglycidyl isocyanurate, described polyfunctional group extend monomer is four-functional group chainextender pyromellitic dianhydride and/or six functional groups chainextender ADR4370.
5. as claimed in claim 1 can the preparation method of foaming PET resin, it is characterized in that: described oxidation inhibitor is antioxidant 1010 and/or irgasfos 168.
6. as claimed in claim 1 can the preparation method of foaming PET resin, it is characterized in that: described thermo-stabilizer is triphenyl phosphite and/or triethylene thiophosphoramide.
7. as claimed in claim 1 can the preparation method of foaming PET resin, it is characterized in that: the described granulation that melt extrudes adopts twin screw extruder to carry out; One district's temperature of described twin screw extruder is 255 ~ 275 DEG C, two district's temperature are 255 ~ 275 DEG C, three district's temperature are 260 ~ 280 DEG C, four district's temperature are 260 ~ 280 DEG C, five district's temperature are 255 ~ 275 DEG C, six district's temperature are 255 ~ 275 DEG C; Described twin screw extruder feeding machine feeding frequency is 10 ~ 20Hz, and main frame rotational frequency is 10 ~ 20Hz.
8. as claimed in claim 1 can the preparation method of foaming PET resin, it is characterized in that: before carrying out described solid phase polycondensation, described material is 100 ~ 120 DEG C of drying 10 ~ 15h in convection oven first, are then transferred in vacuum drying oven, 100 ~ 120 DEG C of vacuum drying 10 ~ 15h.
9. one kind by the preparation method in claim 1 ~ 8 described in any one obtain can foaming PET resin.
10. as claimed in claim 9 can the purposes of foaming PET resin in PET foam article.
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| CN108219181A (en) * | 2017-12-25 | 2018-06-29 | 上海德亿化工有限公司 | A kind of degradable poly terephthaldehyde acids expanded material and preparation method thereof |
| CN108976427A (en) * | 2018-07-04 | 2018-12-11 | 华东理工大学 | A kind of modified resin, feedstock composition, preparation method, foamed material and application |
| CN109280350A (en) * | 2018-08-09 | 2019-01-29 | 丹阳东润保鲜用品实业有限公司 | A kind of rapid shaping degradable composite material and preparation method thereof |
| CN110382604A (en) * | 2017-03-10 | 2019-10-25 | 阿尔温莱纳股份有限两合公司阿尔普拉工厂 | Prepare the method for foaming granule material and the purposes of the foaming granule material |
| CN110527263A (en) * | 2019-09-18 | 2019-12-03 | 合肥市和裕达塑业有限公司 | A kind of high scratch-resistant physical blowing squeezes out PET and PP composite material and preparation method |
| CN115678242A (en) * | 2022-12-13 | 2023-02-03 | 江苏尚艾新材料科技有限公司 | High-performance low-odor antistatic regenerated PC/ABS alloy material for vehicles and preparation method thereof |
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| WO2017179030A1 (en) * | 2016-04-12 | 2017-10-19 | Nunes Miguel Luis Pereira | Continuous synthetic filament covering made of 100% recycled pet |
| CN110382604A (en) * | 2017-03-10 | 2019-10-25 | 阿尔温莱纳股份有限两合公司阿尔普拉工厂 | Prepare the method for foaming granule material and the purposes of the foaming granule material |
| CN108219181A (en) * | 2017-12-25 | 2018-06-29 | 上海德亿化工有限公司 | A kind of degradable poly terephthaldehyde acids expanded material and preparation method thereof |
| CN108219181B (en) * | 2017-12-25 | 2021-06-11 | 上海德亿化工有限公司 | Degradable polyterephthalic acid foaming material and preparation method thereof |
| CN108976427A (en) * | 2018-07-04 | 2018-12-11 | 华东理工大学 | A kind of modified resin, feedstock composition, preparation method, foamed material and application |
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| CN109280350B (en) * | 2018-08-09 | 2021-08-24 | 束建军 | Rapidly-formed degradable composite material and preparation method thereof |
| CN110527263A (en) * | 2019-09-18 | 2019-12-03 | 合肥市和裕达塑业有限公司 | A kind of high scratch-resistant physical blowing squeezes out PET and PP composite material and preparation method |
| CN115678242A (en) * | 2022-12-13 | 2023-02-03 | 江苏尚艾新材料科技有限公司 | High-performance low-odor antistatic regenerated PC/ABS alloy material for vehicles and preparation method thereof |
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