CN110551277A - PET for foaming, PET foaming material and preparation method of foaming material - Google Patents
PET for foaming, PET foaming material and preparation method of foaming material Download PDFInfo
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- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
Abstract
2 2 2The invention discloses a modified PET, which is a modified PET slice prepared by taking terephthalic acid and ethylene glycol as main raw materials through a direct esterification method, and a stabilizing agent, a branching agent, a nucleating agent and a catalyst are added in the reaction.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer foaming materials, relates to modified PET for foaming, a PET foaming material prepared by taking the modified PET as a raw material and a preparation method thereof, and particularly relates to a PET foaming material based on supercritical CO 2 extrusion foaming and a preparation method thereof.
Background
The polyethylene terephthalate (PET) foam material has the unique advantages of low density, high strength, low water absorption and good sound and heat insulation performance, can achieve the effect of obviously increasing the strength and the rigidity without increasing the weight when being used as a structural foam material, and is widely applied to the fields of wind power, rail traffic, ships and naval vessels and aerospace.
2The conventional PET is a crystalline linear polymer, contains benzene rings on a main chain, has a highly regular molecular chain structure, has higher glass transition temperature and melting point, has lower molecular weight, narrower molecular weight distribution, very low melt viscosity and strength, is difficult to bear tensile stress during bubble growth in a foaming process, and is easy to cause cell breakage, collapse and merging, meanwhile, the conventional PET is extremely easy to degrade in a forming processing process at a temperature higher than the melting point, has low crystallization rate, causes a narrow PET foaming forming processing temperature region, and has a higher technical threshold for realizing continuous industrial production of a foaming process.
disclosure of Invention
The invention aims to provide a modified PET for continuously producing an extruded PET foaming material and a method for continuously producing the extruded PET foaming material by using the modified PET as a raw material and only using supercritical CO 2 as a foaming agent without adding other foaming agents aiming at the defects in the prior art, thereby achieving the purposes of safety and environmental protection and greatly simplifying the production process.
the purpose of the invention is realized by the following technical scheme:
a modified PET is prepared from terephthalic acid and ethanediol through direct esterifying, and adding stabilizer, branching agent, nucleating agent and catalyst.
the direct esterification method comprises esterification reaction, melt polycondensation reaction and solid phase polycondensation reaction; the terephthalic acid, the ethylene glycol, the stabilizer, the branching agent, the nucleating agent and the catalyst are added at the same time for reaction.
The preparation method of the modified PET comprises the following steps: putting terephthalic acid, ethylene glycol, a catalyst, a stabilizer, a branching agent and a nucleating agent into a reaction kettle, carrying out esterification reaction at the temperature of 220-265 ℃, vacuumizing for polycondensation when the water yield reaches more than 95% of the theoretical water yield, carrying out polycondensation for 1h under the conditions that the vacuum degree is 250-600 Pa and the temperature is 265-275 ℃, gradually adjusting the vacuum degree to 10-60 Pa, raising the temperature to 275-285 ℃ for continuous polycondensation reaction, discharging, cooling, granulating and drying when the melt intrinsic viscosity is 0.65-0.75 dl/g, thus obtaining modified PET basic slices; and (3) putting the modified PET basic slices into a rotary drum device, gradually heating and crystallizing, carrying out solid-phase polycondensation reaction at 10-40 Pa and 215-230 ℃ for a certain time, and cooling to obtain the modified PET for foaming.
The intrinsic viscosity of the modified PET is 0.8-1.4 dL/g.
the using amount of the ethylene glycol is 25-40 wt% of the modified PET slice; the usage amount of the terephthalic acid is 55-70 wt% of the modified PET slice.
The catalyst is one or more than two of antimony trioxide, antimony acetate, ethylene glycol antimony, germanium dioxide, tetra-n-butyl titanate, titanium potassium oxalate, manganese acetate and zinc acetate, preferably one or more than two of antimony trioxide, antimony acetate and ethylene glycol antimony; the dosage of the catalyst is 0.015-0.06 wt% of the modified PET slice.
The stabilizer is one or a combination of more of phosphoric acid, polyphosphoric acid, trimethyl phosphate, triphenyl phosphite and other phosphoric acid esters; the dosage of the stabilizer is 0.0035-0.5 wt% of the quality of the modified PET chip.
The branching agent is one or the combination of two of glycerol, pentaerythritol, trimellitic anhydride, pyromellitic anhydride, glycerol carbonate, 5-methyl-5-hydroxymethylene-trimethylene carbonate and 5-ethyl-5-hydroxymethylene-trimethylene carbonate; the amount of the branching agent is 0.01 to 0.8 mol% of the molar amount of terephthalic acid.
The nucleating agent is one or a mixture of more of talcum powder, mica, barium sulfate, calcium carbonate, nano silicon dioxide, boron nitride and titanium dioxide; the using amount of the nucleating agent is 0.035-5 wt% of the modified PET slice.
the quality of the modified PET chips refers to the total amount of reaction products of terephthalic acid and ethylene glycol.
The invention also aims to provide a PET foam material, which is prepared by taking modified PET as a raw material and supercritical CO 2 as a foaming agent through continuous production and extrusion.
the invention also aims to provide a preparation method of the PET foaming material, which comprises the following steps:
Drying the modified PET slices at 100-160 ℃ for 4-8 h to form a foaming raw material;
and (2) adding the foaming raw material into an extruder for continuous extrusion foaming, injecting supercritical CO 2 into the extruder, fully mixing the PET melt and supercritical CO 2 in a static mixer under the gas injection pressure of 4-20 MPa, and performing extrusion foaming molding to obtain the PET foaming material.
The extruder for continuous extrusion foaming is a double-order single-screw-single-screw tandem extruder, a double-order double-screw-single-screw tandem extruder or a single-order single-screw extruder.
the extrusion foaming molding is four-section heating and comprises the following steps:
first zone temperature: 240-280 ℃;
Temperature in the second zone: 250 to 290 ℃;
temperature of the third zone: 220-280 ℃;
Temperature in the fourth zone: 220-280 ℃;
Static mixer temperature: 220-280 ℃;
head temperature: 220 to 280 ℃.
Preferably, the extrusion foaming molding is four-stage heating, which respectively comprises the following steps:
first zone temperature: 240-260 ℃;
Temperature in the second zone: 260-280 ℃;
Temperature of the third zone: 250-270 ℃;
Temperature in the fourth zone: 230-260 ℃;
Static mixer temperature: 220-260 ℃;
Head temperature: 220 to 260 ℃.
By adopting the temperature setting, on one hand, the modified PET material is fully plasticized, so that the supercritical CO 2 and the modified PET melt are uniformly mixed, the viscosity and the strength of the melt are ensured, and the foaming molding is facilitated.
Compared with the prior art, the invention has the beneficial effects that:
the branched modified PET with high viscosity and high melt strength is prepared by combining the branching technology with the solid phase polycondensation reaction technology, simultaneously meets the crystallization performance requirement of the foaming process, can be directly subjected to supercritical CO 2 extrusion foaming processing, is highly continuous and stable in production process, safe and free of environmental pollution, is simpler and more convenient in foaming process, is suitable for industrial scale production, is only supercritical CO 2 as the foaming agent, is free of other foaming agents, and has no influence on the use performance and use safety of the product.
The prepared PET foam material has medium and high foaming multiplying power, excellent cell size distribution, 60-90 kg/m 3 apparent density range, 6 x 10 11 -8 x 10 11/cm 3 cell density range and good mechanical property, and the PET foam material product can be widely applied to buildings, decorative materials (such as heat insulation materials and high-grade decorative materials replacing wood), wind power blade supporting and filling materials, structural materials of high-speed trains, ships, airplanes and public transportation systems, ground covering materials, such as floors, outdoor products and the like.
Drawings
FIG. 1 is a scanning electron micrograph of the PET foam obtained in example 1.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments. It should be understood that the following examples are illustrative of the present invention only and are not intended to limit the scope of the present invention. After reading the teaching of the present invention, the skilled in the art can make various changes or modifications to the invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1
Placing 30kg of ethylene glycol, 60kg of terephthalic acid, 13.88g of antimony trioxide, 3.47g of triphenyl phosphite, 5g of pentaerythritol and 200g of talcum powder in a 150L stainless steel reaction kettle, heating for esterification, wherein the esterification temperature is 220-265 ℃, vacuumizing for polycondensation when the water yield reaches more than 95% of the theoretical water yield, performing polycondensation for 1h under the conditions of a vacuum degree of 250-600 Pa and a temperature of 265-275 ℃, gradually switching to a vacuum degree of 10-60 Pa, raising the temperature to 275-285 ℃ for continuous polycondensation reaction, discharging, cooling, granulating and drying when the melt intrinsic viscosity is 0.65-0.75 dL/g, thus obtaining a modified PET basic slice; 32kg of modified PET basic slices are put into a 100L rotary drum device, after gradually heating up and crystallizing, the solid phase polycondensation reaction is carried out at 20Pa and 225 ℃, and the modified PET for foaming with the intrinsic viscosity of 1.40dL/g is obtained after cooling.
Drying the modified PET slices at 140 ℃ for 4 hours, adding the slices into an extruder for continuous extrusion foaming, injecting supercritical CO 2 into the extruder, injecting gas at a pressure of 4.0MPa, fully mixing, and performing extrusion foaming molding to obtain the PET foamed material, wherein the extrusion temperature is 260 ℃ in a first region, 280 ℃ in a second region, 270 ℃ in a third region, 250 ℃ in a fourth region, 235 ℃ in a static mixer, 220 ℃ in a machine head, and the apparent density of the PET foamed material is 90kg/m 3.
Example 2
placing 30kg of ethylene glycol, 60kg of terephthalic acid, 40g of antimony acetate, 6g of triphenyl phosphate, 266g of glycerol and 3400g of barium sulfate in a 150L stainless steel reaction kettle, heating for esterification, wherein the esterification temperature is 220-265 ℃, when the water yield reaches more than 95% of the theoretical water yield, vacuumizing for polycondensation, carrying out polycondensation for 1h under the conditions of a vacuum degree of 250-600 Pa and a temperature of 265-275 ℃, gradually switching to a vacuum degree of 10-60 Pa, raising the temperature to 275-285 ℃ for continuous polycondensation reaction, discharging, cooling, granulating and drying when the melt intrinsic viscosity is 0.65-0.75 dL/g, thus obtaining a modified PET basic slice; 32kg of modified PET basic slices are put into a 100L rotary drum device, after gradually heating up and crystallizing, the solid phase polycondensation reaction is carried out at 40Pa and 215 ℃, and the modified PET for foaming with the intrinsic viscosity of 0.80dL/g is obtained after cooling.
Drying the modified PET at 130 ℃ for 4h, adding the dried modified PET into an extruder for continuous extrusion foaming, injecting supercritical CO 2 into the extruder, fully mixing the dried modified PET with a gas injection pressure of 20MPa, and performing extrusion foaming to obtain the PET foamed material, wherein the extrusion temperature is 255 ℃ in a first region, 280 ℃ in a second region, 265 ℃ in a third region, 260 ℃ in a fourth region, 240 ℃ in a static mixer, 240 ℃ in a machine head, and the apparent density of the PET foamed material is 68kg/m 3.
Example 3
Placing 80kg of ethylene glycol, 150kg of terephthalic acid, 48g of ethylene glycol antimony, 270g of triphenyl phosphite, 87g of pentaerythritol and 86.8g of boron nitride in a 300L stainless steel reaction kettle, heating for esterification, wherein the esterification temperature is 220-265 ℃, when the water yield reaches more than 95% of the theoretical water yield, vacuumizing for polycondensation, carrying out polycondensation for 1h under the conditions of a vacuum degree of 250-600 Pa and a temperature of 265-275 ℃, gradually switching to a vacuum degree of 10-60 Pa, raising the temperature to 275-285 ℃ for continuous polycondensation reaction, discharging, cooling, granulating and drying when the melt intrinsic viscosity is 0.65-0.75 dL/g, thus obtaining a modified PET basic slice; 120kg of modified PET basic slices are put into a 600L rotary drum device, after gradually heating up and crystallizing, the solid phase polycondensation reaction is carried out at 20Pa and 220 ℃, and the modified PET for foaming with the intrinsic viscosity of 1.25dL/g is obtained after cooling.
drying the modified PET at 140 ℃ for 4h, adding the dried modified PET into an extruder for continuous extrusion foaming, injecting supercritical CO 2 into the extruder, and fully mixing the materials under the gas injection pressure of 10MPa to extrude and foam the PET foamed material, wherein the extrusion temperature is 255 ℃ in a first region, 275 ℃ in a second region, 260 ℃ in a third region, 250 ℃ in a fourth region, 230 ℃ in a static mixer, 228 ℃ in a machine head, and the apparent density of the PET foamed material is 74kg/m 3.
example 4
putting 78kg of ethylene glycol, 150kg of terephthalic acid, 50g of ethylene glycol antimony, 12.0g of phosphoric acid, 125g of pentaerythritol, 350g of talcum powder and 200g of nano-silica into a 300L stainless steel reaction kettle, heating for esterification, wherein the esterification temperature is 220-265 ℃, when the water yield reaches more than 95% of the theoretical water yield, vacuumizing for polycondensation, carrying out polycondensation for 1 hour under the conditions of a vacuum degree of 250-600 Pa and a temperature of 265-275 ℃, gradually switching to a vacuum degree of 10-60 Pa, heating to 275-285 ℃ for polycondensation reaction, discharging, cooling, granulating and drying when the melt intrinsic viscosity is 0.65-0.75 dL/g, thus obtaining a modified PET basic slice; 120kg of modified PET basic slices are put into a 600L rotary drum device, after gradually heating up and crystallizing, the solid phase polycondensation reaction is carried out at 20Pa and 218 ℃, and the modified PET for foaming with the intrinsic viscosity of 1.20dL/g is obtained after cooling.
Drying the modified PET at 140 ℃ for 4h, adding the dried modified PET into an extruder for continuous extrusion foaming, injecting supercritical CO 2 into the extruder, and fully mixing the materials under the gas injection pressure of 20MPa to extrude and foam the PET foamed material, wherein the extrusion temperature is 240 ℃ in the first region, 280 ℃ in the second region, 260 ℃ in the third region, 250 ℃ in the fourth region, 235 ℃ in a static mixer, 232 ℃ in a machine head, and the apparent density of the PET foamed material is 60kg/m 3.
Example 5
Putting 78kg of ethylene glycol, 150kg of terephthalic acid, 48g of ethylene glycol antimony, 12.0g of phosphoric acid, 49.2g of pentaerythritol and 100g of boron nitride into a 300L stainless steel reaction kettle, heating for esterification, wherein the esterification temperature is 220-265 ℃, vacuumizing for polycondensation when the water yield reaches more than 95% of the theoretical water yield, performing polycondensation for 1h under the conditions of a vacuum degree of 250-600 Pa and a temperature of 265-275 ℃, gradually switching to a vacuum degree of 10-60 Pa, heating to 275-285 ℃ for polycondensation reaction, discharging, cooling, granulating and drying when the melt intrinsic viscosity is 0.65-0.75 dL/g, thus obtaining a modified PET basic slice; 120kg of modified PET basic slices are put into a 600L rotary drum device, after gradually heating up and crystallizing, the solid phase polycondensation reaction is carried out at 10Pa and 230 ℃, and the modified PET for foaming with the intrinsic viscosity of 1.15dL/g is obtained after cooling.
Drying the modified PET at 140 ℃ for 4 hours, adding the dried modified PET into an extruder for continuous extrusion foaming, injecting supercritical CO 2 into the extruder, and fully mixing the materials under the gas injection pressure of 7.5MPa to extrude and foam the PET foamed material, wherein the extrusion temperature is 245 ℃ in a first region, 278 ℃ in a second region, 262 ℃ in a third region, 255 ℃ in a fourth region, 240 ℃ in a static mixer, 235 ℃ in a machine head, and the apparent density of the PET foamed material is 80kg/m 3.
Example 6
Putting 78kg of ethylene glycol, 150kg of terephthalic acid, 52g of ethylene glycol antimony, 18.0g of trimethyl phosphate, 87g of pentaerythritol and 350g of talcum powder into a 300L stainless steel reaction kettle, heating for esterification, wherein the esterification temperature is 220-265 ℃, when the water yield reaches more than 95% of the theoretical water yield, vacuumizing for polycondensation, carrying out polycondensation for 1h under the conditions of a vacuum degree of 250-600 Pa and a temperature of 265-275 ℃, gradually switching to a vacuum degree of 10-60 Pa, raising the temperature to 275-285 ℃ for continuous polycondensation, discharging, cooling, granulating and drying when the melt intrinsic viscosity is 0.65-0.75 dL/g, thus obtaining a modified PET basic slice; 120kg of modified PET basic slices are put into a 600L rotary drum device, after gradually heating up and crystallizing, the solid phase polycondensation reaction is carried out at 40Pa and 225 ℃, and the modified PET for foaming with the intrinsic viscosity of 1.34dL/g is obtained after cooling.
drying the modified PET at 130 ℃ for 4h, adding the dried modified PET into an extruder for continuous extrusion foaming, injecting supercritical CO 2 into the extruder, and fully mixing the materials under the gas injection pressure of 15MPa to extrude and foam the PET foamed material, wherein the extrusion temperature is 240 ℃ in the first region, 275 ℃ in the second region, 260 ℃ in the third region, 245 ℃ in the fourth region, 238 ℃ in a static mixer, 240 ℃ in a machine head, and the apparent density of the PET foamed material is 63kg/m 3.
Example 7
putting 78kg of ethylene glycol, 150kg of terephthalic acid, 34.7g of ethylene glycol antimony, 15.0g of trimethyl phosphate, 980g of pentaerythritol and 200g of boron nitride into a 300L stainless steel reaction kettle, heating for esterification, wherein the esterification temperature is 220-265 ℃, vacuumizing for polycondensation when the water yield reaches more than 95% of the theoretical water yield, performing polycondensation for 1h under the conditions of a vacuum degree of 250-600 Pa and a temperature of 265-275 ℃, gradually switching to a vacuum degree of 10-60 Pa, heating to 275-285 ℃ for polycondensation reaction, discharging, cooling, granulating and drying when the melt intrinsic viscosity is 0.65-0.75 dL/g, thereby obtaining a modified PET basic slice; 120kg of modified PET basic slices are put into a 600L rotary drum device, after gradually heating up and crystallizing, the solid phase polycondensation reaction is carried out at 40Pa and 215 ℃, and the modified PET for foaming with the intrinsic viscosity reaching 0.80dL/g is obtained after cooling.
drying the modified PET at 140 ℃ for 4h, adding the dried modified PET into an extruder for continuous extrusion foaming, injecting supercritical CO 2 into the extruder, and fully mixing the materials under the gas injection pressure of 15MPa to extrude and foam the PET foamed material, wherein the extrusion temperature is 240 ℃ in the first region, 275 ℃ in the second region, 260 ℃ in the third region, 245 ℃ in the fourth region, 260 ℃ in a static mixer, 260 ℃ in a machine head, and the apparent density of the PET foamed material is 85kg/m 3.
comparative example 1
Putting 78kg of ethylene glycol, 150kg of terephthalic acid, 34.7g of ethylene glycol antimony and 15.0g of trimethyl phosphate into a 300L stainless steel reaction kettle, heating for esterification, wherein the esterification temperature is 220-265 ℃, vacuumizing for polycondensation when the water yield reaches more than 95% of the theoretical water yield, performing polycondensation for 1h under the conditions of the vacuum degree of 250-600 Pa and the temperature of 265-275 ℃, gradually switching to the vacuum degree of 10-60 Pa, raising the temperature to 275-285 ℃ for continuous polycondensation, discharging, cooling, granulating and drying when the melt intrinsic viscosity is 0.65-0.75 dl/g, so as to obtain a PET basic slice; and (3) putting 120kg of PET basic slices into a 600L rotary drum device, gradually heating and crystallizing, carrying out solid-phase polycondensation reaction at 10Pa and 225 ℃, and cooling to obtain the high-viscosity PET with the intrinsic viscosity of 1.00 dL/g.
Drying the high-viscosity PET at 140 ℃ for 4h, adding the high-viscosity PET into an extruder for continuous extrusion foaming, injecting supercritical CO 2 into the extruder, and performing an extrusion foaming test, wherein the foam holes of the extruded material are difficult to stably form at different extrusion process temperatures, and the foam material with relatively uniform foam holes is difficult to obtain.
Claims (10)
1. the modified PET is characterized in that the modified PET is a modified PET slice prepared by taking terephthalic acid and ethylene glycol as main raw materials and adopting a direct esterification method, wherein a stabilizer, a branching agent, a nucleating agent and a catalyst are added in the reaction process.
2. The modified PET as claimed in claim 1, wherein the direct esterification process comprises esterification, melt polycondensation and solid phase polycondensation; the terephthalic acid, the ethylene glycol, the stabilizer, the branching agent, the nucleating agent and the catalyst are added at the same time for reaction.
3. The modified PET as claimed in claim 1, which is prepared by the following process: putting terephthalic acid, ethylene glycol, a stabilizer, a branching agent, a nucleating agent and a catalyst into a reaction kettle, carrying out esterification reaction at the temperature of 220-265 ℃, vacuumizing for polycondensation when the water yield reaches more than 95% of the theoretical water yield, carrying out polycondensation for 1h under the conditions of a vacuum degree of 250-600 Pa and a temperature of 265-275 ℃, gradually adjusting the vacuum degree to 10-60 Pa, raising the temperature to 275-285 ℃, discharging, cooling, granulating and drying when the melt intrinsic viscosity is 0.65-0.75 dl/g, thus obtaining modified PET basic slices; and (3) putting the modified PET basic slices into a rotary drum device, gradually heating and crystallizing, carrying out solid-phase polycondensation reaction at 10-40 Pa and 215-230 ℃, and cooling after the reaction is finished to obtain the modified PET for foaming.
4. the modified PET as claimed in claim 1, wherein the modified PET has an intrinsic viscosity of 0.8 to 1.4 dL/g.
5. The modified PET as claimed in claim 1, wherein the amount of the ethylene glycol is 25-40 wt% of the modified PET chip; the usage amount of the terephthalic acid is 55-70 wt% of the modified PET slice.
6. The modified PET as claimed in claim 1, wherein the catalyst is one or more of antimony trioxide, antimony acetate, ethylene glycol antimony, germanium dioxide, tetra-n-butyl titanate, titanium potassium oxalate, manganese acetate and zinc acetate, preferably one or more of antimony trioxide, antimony acetate and ethylene glycol antimony; the amount of the catalyst is 0.015-0.06 wt% of the mass of the modified PET slice;
the stabilizer is one or a combination of more of phosphoric acid, polyphosphoric acid, trimethyl phosphate, triphenyl phosphite and other phosphoric acid esters; the using amount of the stabilizer is 0.0035-0.5 wt% of the modified PET slice quality;
the nucleating agent is one or a mixture of more of talcum powder, mica, barium sulfate, calcium carbonate, nano silicon dioxide, boron nitride and titanium dioxide; the using amount of the nucleating agent is 0.035-5 wt% of the modified PET slice.
7. the modified PET as claimed in claim 1, wherein the branching agent is one or a combination of glycerol, pentaerythritol, trimellitic anhydride, pyromellitic anhydride, glycerol carbonate, 5-methyl-5-hydroxymethylene-trimethylene carbonate and 5-ethyl-5-hydroxymethylene-trimethylene carbonate; the amount of the branching agent is 0.01 to 0.8 mol% of the molar amount of terephthalic acid.
8. The PET foam material is characterized in that the PET foam material is obtained by taking modified PET as a raw material and supercritical CO 2 as a foaming agent through continuous production and extrusion.
9. The method for preparing PET foamed material according to claim 8, characterized by comprising the steps of:
Drying the modified PET slices at 100-160 ℃ for 4-8 h to form a foaming raw material;
Adding a foaming raw material into an extruder for continuous extrusion foaming, injecting supercritical CO 2 into the extruder, fully mixing a PET melt and supercritical CO 2 in a static mixer under the gas injection pressure of 4-20 MPa, and performing extrusion foaming molding to obtain a PET foaming material;
The extrusion foaming molding is four-section heating and comprises the following steps:
first zone temperature: 240-280 ℃;
Temperature in the second zone: 250 to 290 ℃;
Temperature of the third zone: 220-280 ℃;
Temperature in the fourth zone: 220-280 ℃;
Static mixer temperature: 220-280 ℃;
Head temperature: 220 to 280 ℃.
10. The method for preparing PET foaming material according to claim 9, characterized in that the extrusion foaming molding is four-stage heating, which comprises:
First zone temperature: 240-260 ℃;
temperature in the second zone: 260-280 ℃;
Temperature of the third zone: 250-270 ℃;
temperature in the fourth zone: 230-260 ℃;
Static mixer temperature: 220-260 ℃;
Head temperature: 220 to 260 ℃.
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