CN101544811A - Foaming PET sheet material and method for preparing same - Google Patents
Foaming PET sheet material and method for preparing same Download PDFInfo
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- CN101544811A CN101544811A CN200910302063A CN200910302063A CN101544811A CN 101544811 A CN101544811 A CN 101544811A CN 200910302063 A CN200910302063 A CN 200910302063A CN 200910302063 A CN200910302063 A CN 200910302063A CN 101544811 A CN101544811 A CN 101544811A
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Abstract
The invention belongs to high molecule material technology field, especially a foaming PET sheet material and a method for preparing the same. The invention provides a forming PET sheet material, which is produced by uniformly mixing 100 portions of bottle grade PET, 0.1-40 portions of blowing promoter and 0.1-10 portions of foaming agent, extruding and forming. The blowing promoter is prepared by uniformly mixing 0.1-30 portions of acrylic ester multiple copolymers, 0.1-10 portions of polyfunctional group substance with high activity and 10-100 portions of carrier resin. The invention adopts blowing promoter to mildly crosslink PET or form a branched structure, improves or stabilizes the melt strength of the bottle grade PET, obtains the foamed PET sheet materials with the finished product density range of 0.60-0.95 g/cm[3] and is suitable for producing food trays, medicine trays, electric product trays and the like.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly foaming PET sheet material and preparation method thereof.
Background technology
PET (polyethylene terephthalate) resin has up to ten million tons output in China, because output is big, price is relatively stable.PET is in historic high price a few years ago, and comparing with PS (polystyrene) does not have price advantage, and this has limited its substituting PS in packaging field.The density of PET is 1.33g/cm in addition
3, than the density 1.05g/cm of PS
3Much higher, usually adopt high the filling or foaming method for this reason, make density reduce and reach the not 50-60% of foamex density, drop to and can compete with current cost with PS.It is worthy of note, after the PET foaming, can reduce the weight of packing, can alleviate impact, help energy-saving and emission-reduction environment.
All business-like foaming PETs all adopt pneumatogen in the U.S., and the most chemical foaming agents that adopt in Europe.Foam sheet can become pallet by plastic uptake, is used for food, medicine or electronic product packing.Physical blowing need adopt high-tension apparatus, and main difficult point is equipment.And chemical foaming can adopt general PET sheet material extrusion equipment, and cost of investment is low.Sheet material of the present invention mainly adopts chemical blowing process.
Chemical foaming agent can be divided into organic and inorganic two classes.The organic chemistry whipping agent is various in style, because the PET processing temperature is higher, mainly adopts high-temperature foaming agent.Inorganic foaming agent the earliest such as carbonate and supercarbonate are replaced by the supercarbonate of better effects and if citric acid system through modification.Better foaming system is Polycarbonic acids and carbonate mixture, belongs to the thermo-negative reaction type, can solve this big problem of heat radiation in the foaming process.
Foaming PET has the following advantages:
1, the PET foam has the ideal dimensional stability, to O
2, CO
2The barrier good, good wear resistance and surperficial retardation capability with steam.These products also have anti-ethanol, oils, fat and rare mineral oil, diluted acid, diluted alkaline, salt and the soap of height.
2, has high rate of closed hole.
3, thermostability: about 200 ℃ of PET foam maximum operation temperature, and the working temperature of polystyrene foam has only 70 ℃, about 100 ℃ of urethane and PVC foam.PET foamy dimensional stability is all better than other foam.
4, mechanical property: wanting of PET foamy mechanical property ratio PS, PU foam and glass foam is high.
5, water absorbing properties: water-absorbent is lower than urethane, expanded polystyrene foam, and is suitable with XEPS (extruded polystyrene heat insulating board, Extruded Polystyrene Insulation).
6, steam transmitance: the diffusion of its steam stops coefficient μ high 10 times than elastomer foam, high 100 times than other foams plastic material.
Just because of above-mentioned good barrier property, mechanical property, chemicals-resistant and resistance toheat, the foaming PET material is the ideal material of food product pack.PET multipolymer and intrinsic viscosity (IV, intrinsic viscosity number) are though can foam greater than the sticking PET of the height of 1.0dl/g at present, and cost is higher.Have only the lower conventional bottle level PET foaming of the price utilized, could obtain competitive edge.But the melt viscosity of expanded plastic is most important to forming stabilise bubbles.Since viscosity problem, and do not find suitable process window, before polymkeric substance solidifies, fail to allow bubble fully cool off and cause bubble collapse, so wish to utilize the never success of effort of bottle level even the foaming of fiber level PET in the prior art.
Summary of the invention
First technical problem to be solved by this invention provides a kind of PET sheet material that utilizes bottle level PET foaming preparation, this foaming PET sheet material specifically is by 100 parts of bottle level PETs, add 0.1～40 part of frothing aid and 0.1～10 part of whipping agent mixing, extrusion moulding obtains;
Described frothing aid is prepared from by the raw material blending of following weight part:
0.1 the esters of acrylic acid material of～30 parts of ethylene-acrylate-glycidyl methacrylate terpolymers or nucleocapsid structure,
0.1～10 parts of high reactivity polyfunctional group materials,
10～100 parts of vector resins;
Wherein, the esters of acrylic acid material of described nucleocapsid structure is vinylformic acid or acrylate and the crosslinked product of styrene-butadiene rubber(SBR), and case material band functional group is grafted on the rubber of core body, forms a kind of two-phase separated structures;
Described vector resin is close with the processing temperature of bottle level PET (270～310 ℃ of processing temperatures), and thermotolerance is higher, and 300 ℃ are not decomposed more than the 10min, have high flowability, and melt index is the resinoid of 5～150g/10min.For example, polyolefin resin (PE and PP etc.), polycarbonate resin, conjugated polyester resin or nylon resin.
Described high reactivity polyfunctional group material is anhydrides (at least a in), oxazole class (shown in the formula 3) shown in formula 1, the formula 2, hexanolactam class (shown in the formula 4), epoxy resin (shown in formula 5, the formula 6), the triphenyl phosphite (shown in the formula 7).
Formula 1
Formula 2
Formula 3
Formula 4
Formula 5
Formula 6
Formula 7
Described whipping agent can adopt PET to use whipping agent always.
Further, the IV value of described bottle level PET is 0.70～1.40dl/g.
The present invention adopts the lightly crosslinked bottle level PET of frothing aid or forms branched structure, and the melt strength of raising or stable bottle level PET obtains foaming PET sheet material after the foaming.Foaming PET sheet material finished product density scope of the present invention is 0.60-0.95g/cm
3
Second technical problem to be solved by this invention provides the preparation method of above-mentioned foaming PET sheet material, specifically may further comprise the steps:
A, 0.1～30 part of acrylate multipolymer, 0.1～10 part of high reactivity polyfunctional group material and 10～100 parts of vector resins mix, and extruding pelletization under the melt temperature of vector resin is made frothing aid;
B, frothing aid are at 60 ℃～120 ℃ dry 4h;
C, 100 parts of bottle level PETs add extrusion moulding behind the frothing aid of 0.1～40 part of step B and 0.1～10 part of whipping agent mixing.
The present invention makes the method for foaming PET sheet material, adopts multiple means to improve melt viscosity and the intensity of PET, can extrusion moulding obtains the foaming PET sheet material of excellent property.The means that adopted comprise, thereby one, improve the PET molecular weight and improve melt viscosity and intensity, guarantee that gas that foaming produces can be coated in the melt and do not overflow rapidly; Two, improve the toughness of PET, toughness and high molecular, high viscosity link together, thereby can keep the foamed gas in the melt, form stable foam.The approach that improves molecular weight is a polyfunctional group high reactivity material, at once increase substantially the molecular weight of PET in they or they the process that is combined in extrusion sheet, make PET branchign of molecule or lightly crosslinked, thereby improve viscosity and intensity, can stablize the gas that keeps whipping agent decomposition generation in a large number, form stable foam.
Description of drawings
Fig. 1 is the structural representation of the acrylate multipolymer of nucleocapsid structure.
Fig. 2 is foaming PET sheet material thermal treatment flow process figure, and 1 is formpiston, and 2 is former.
Embodiment
The present invention improves melt viscosity in extrusion foaming PET sheet material process and thereby intensity makes the gas of whipping agent generation remain in the stable foamy structure of formation in the sheet base, this foaming PET sheet material specifically is by 100 parts of bottle level PETs, add 0.1～40 part of frothing aid and 0.1～10 part of whipping agent mixing, extrusion moulding obtains; Described frothing aid is that the raw material blending by following weight part is prepared from:
0.1 the esters of acrylic acid material of～30 parts of ethylene-acrylate-glycidyl methacrylate terpolymers or nucleocapsid structure,
0.1～10 parts of high reactivity polyfunctional group materials,
10～100 parts of vector resins;
The structure of the acrylate multipolymer of described nucleocapsid structure as shown in Figure 1, core body wherein is a cross-linked rubber, as vinylformic acid or acrylate and the crosslinked product of styrene-butadiene rubber(SBR), and case material band functional group, be grafted on the rubber of core body, form a kind of two-phase separated structures, make the existing good consistency of this material, can absorb impact energy again, reach the purpose of impact modification.Can obtain the material of different shock resistances by the content of regulating the esters of acrylic acid material in the multiple copolymer, can eliminate the fragility of conventional bottle level PET, improve its toughness, the fragility when particularly improving the scrap stock reuse after the foaming PET sheet material thermoforming.
Described vector resin is close with the processing temperature of bottle level PET (270～310 ℃ of processing temperatures), and thermotolerance is higher, and 300 ℃ are not decomposed more than the 10min, have high flowability, and melt index is the resinoid of 5～150g/10min.For example, polyolefin resin, conjugated polyester resin, PBT resin, nylon resin or polycarbonate resin.Be preferably a kind of in PP resin, Nylon 6, LDPE resin, the PETG resin.
Described high reactivity polyfunctional group material is anhydrides (at least a in), oxazole class (shown in the formula 3) shown in formula 1, the formula 2, hexanolactam class (shown in the formula 4), epoxy resin (shown in formula 5, the formula 6), the triphenyl phosphite (shown in the formula 7).
Preferably, foaming PET sheet material of the present invention is by 100 parts of bottle level PETs, adds 0.1～20 part of frothing aid and 0.1～5 part of whipping agent mixing, and extrusion moulding obtains.
Described whipping agent can adopt PET to use whipping agent always, is preferably AZNP (azodicarbonamide), 5PT (5-phenyltetrazole), or supercarbonate and citric acid mixture.
Further, the IV value of described bottle level PET is 0.70～1.40dl/g, and foaming effect was bad when the IV value was lower than 0.70dl/g, and when being higher than 1.40dl/g, cost is too high.
The preparation method of foaming PET sheet material of the present invention specifically may further comprise the steps:
A, 0.1～30 part of acrylate multipolymer, 0.1～10 part of high reactivity polyfunctional group material and 10～100 parts of vector resins mix, and extruding pelletization under the melt temperature of vector resin is made frothing aid;
B, frothing aid are at 60 ℃～120 ℃ dry 4h;
C, 100 parts of bottle level PETs add extrusion moulding behind the frothing aid of 0.1～40 part of step B and 0.1～10 part of whipping agent mixing.
Can add toner in the frothing aid, play and adjust the sheet material color, make its effect attractive in appearance, described toner, at industrial main application carbon black, titanium dioxide, the color that also can adopt other to need, but used toner must have higher thermotolerance, in order to avoid influence the thermotolerance of sheet material.
(30ppm～50ppm) can cause the sizable reduction of IV value of PET to a spot of moisture.Therefore bottle level PET requires moisture below 30ppm with before frothing aid and whipping agent mix.PET needs at 160 ℃ of dryings 4h at least.When dry, use the highest-35 ℃ air of dew point, preferably select the dry air hopper of continuous high temperature dehumidification type for use, the subsidiary regeneration of hopper desiccant bed.
The PET melt Conveying that has been full of gas needs higher melt pressure during to extrusion neck ring mold, and to prevent pre-frothing in the mouth mould, the consequence of mouthful foam-in-mould is that the surface quality of the finished product is very poor, the fibrosis phenomenon occurs in mouth mould exit.
The extrusion moulding of PET foamy can be adopted twin screw, second order list screw rod and three kinds of equipment of tandem.Standard P ET plasticizing extrusion temperature be 200 ℃-280 ℃-270 ℃-up to the Melt Pump section.In the PET foaming process, to avoid excessive shear, otherwise can thermal destruction.
After the heating of foaming PET sheet process, moulding, the further processing (die-cut, pile), the scrap stock of receiving in a large number (generally up to 50%).Do not recycle and can cause waste, after the PET foaming was extruded, the IV value can descend, and what for example have has been reduced to 0.62 from 0.80; Perhaps be reduced to about 0.95 from primary 1.05.For this reason, can adopt the mode of adding high reactivity polyfunctional group material (formula 1 is to compound shown in the formula 7) to improve the IV value and the melt strength of scrap stock.
Scrap stock add high reactivity polyfunctional group material in the process of foaming, extruding pelletization once more after, high reactivity polyfunctional group material can with the hydroxyl or the carboxyl reaction of scrap stock, the end of the chain of high reactivity polyfunctional group material rides over the end of PET molecule, forms a kind of star-like cladodification molecule by the lengthening chain length and the degree of branching.Again the IV value of PET has been brought up to the IV value level of former raw material or higher after the granulation, thereby improves melt viscosity and intensity.Can guarantee like this to have added scrap stock the PET extrusion and foaming process smoothly, can guarantee that also the performance behind the sheet material plastics sucking moulding satisfies service requirements.The recoverying and utilizing method of scrap stock is specially (by weight): 50 parts of foaming PET sheet material corner returns, 50 parts, 0.1～5 part whipping agent of bottle level PET and 20～40 parts of frothing aid mixings, extrusion moulding promptly.
The invention will be further elaborated below in conjunction with embodiment.Embodiment only is used to illustrate the present invention, rather than limits the present invention by any way.
Embodiment one stablizes the preparation of the frothing aid of PET foamy structure
Vector resin is the PP resin, and its melting index is 150g/10min, and the PP resin is in advance more than 80～110 ℃ of dry 2h.100 parts of acrylate multipolymers of 100 parts of dried pp resins and 10 parts of hexanolactam compounds shown in the formula 3, nucleocapsid structure (for example Rohm Haas company produce EXL-2600) and carbon black mix 8～10min for 20 parts in high-speed mixer, again with twin screw extruder under 160～230 ℃, extrude, pelletizing, drying, it is standby to be cooled to the packing of back below 60 ℃.
Embodiment two stablizes the preparation of the frothing aid of PET foamy structure
With the Nylon 6 is vector resin, its melting index is 5g/10min, Nylon 6 is earlier at 100～110 ℃ of drying 6～8h, 80 parts of dried Nylon 6s mix 8～10min for 15 parts with 12 parts of triphenyl phosphites, 120 parts of ethylene-acrylate-glycidyl methacrylate (for example LOTADER GMA AX8900 of Total company), titanium dioxide in high-speed mixer, again with twin screw extruder under 230～260 ℃, extrude, pelletizing, drying, it is standby to be cooled to the packing of back below 60 ℃.
Embodiment three stablizes the preparation of the frothing aid of PET foamy structure
After 15 parts of 6 parts of Resins, epoxy compounds shown in 100 parts of LDPE resins (melting index is 5g/10min), the formula 4,60 parts of ethylene-acrylate glycidyl methacrylate examples (as the LOTADER GMA AX8840 of Total company), carbon black mix in high-speed mixer, in high-power pair of vacuum twin screw extruder, under 160～240 ℃, extrude, pelletizing, drying, it is standby to be cooled to the packing of back below 60 ℃.
Embodiment four stablizes the preparation of the frothing aid of PET foamy structure
After 14 parts of 120 parts of the acrylate multipolymers of 100 parts of PETG resins (melting index is 30g/10min), formula 2 is shown 18 parts of oxazole compounds, nucleocapsid structure (for example Rohm Haas company produce TS-7200), titanium dioxide mix in high-speed mixer, in high-power pair of vacuum twin screw extruder, in 220～270 ℃ of following extruding pelletizations, pelletizing, drying, be cooled to back below 60 ℃ and pack standby.
The preparation of embodiment five foaming PET sheet materials
The frothing aid that embodiment one prepares is more than 60 ℃ of dry 2h.
The drying of the bottle level PET of IV value 0.95: 175 ℃ of air themperature, time of drying 5～6h, minimum airshed 0.7m
3/ h per kilogram resin.
In 100 parts of above-mentioned bottle level PETs, add 0.1 part of frothing aid and 0.3 part of supercarbonate/citric acid system whipping agent that drying is good, to be full of the extrusion neck ring mold place extrusion moulding of the PET melt Conveying of gas to single screw rod sheet extruder then, extruder temperature control is as follows:
Machine barrel: 260～270 ℃; Adapter temperature: 265 ℃; The mouth mould: 255 ℃, 245 ℃=die lip temperature; Bowl temperature: cylinder 1 is 30 ℃, and cylinder 2 is 40 ℃, and cylinder 3 is 55 ℃.
The sheet material density of producing is 0.80g/cm
3Its tensile property sees Table 1.
Table 1 sheet material tensile property
The plastic-sucking tray that prepared sheet material is suitable as pharmaceutical prod uses.
The preparation of embodiment six foaming PET sheet materials
The frothing aid that embodiment two prepares is more than 100 ℃ of dry 2h.
The drying of the bottle level PET of IV value 1.25: 175 ℃ of air themperature, time of drying 5～6h, minimum airshed 0.7m
3/ h per kilogram resin.
Add 3 parts of frothing aid and 0.5 part of whipping agent 5PT that drying is good in 100 parts of above-mentioned PET, the PET melt (being heated to 185 ℃) that will be full of gas then is transported to the extrusion neck ring mold place extrusion moulding of single screw rod sheet extruder, and extruder temperature is as follows;
Machine barrel: 260-270 ℃; Adapter temperature: 260 ℃; The mouth mould: 250 ℃, 245 ℃=die lip temperature; Bowl temperature: cylinder 1 is 30 ℃, and cylinder 2 is 40 ℃, and cylinder 3 is 55 ℃.
The sheet material density of producing is 0.75g/cm
3Its tensile property sees Table 2.
Table 2 sheet material tensile property
The plastic-sucking tray that prepared sheet material is suitable as electronic product uses.
The preparation of embodiment seven foaming PET sheet materials
The drying of the bottle level PET of IV value 0.80: 175 ℃ of air themperature, time of drying 5～6h, minimum airshed 0.7m
3/ h per kilogram resin.The frothing aid that embodiment three prepares is in 60 ℃ of dry 4h.
Add 10 parts of frothing aid and 0.1 part of whipping agent 5PT that drying is good in 100 parts of above-mentioned PET, the PET melt (being heated to 185 ℃) that will be full of gas then is transported to the extrusion neck ring mold place extrusion moulding of single screw rod sheet extruder, extrusion moulding by the following method:
-extrude line: use single screw rod PET forcing machine, metering of band whipping agent and drying plant.
-forcing machine, mouthful mould and three rod cylinders: identical with common PET sheet production equipment.
Extruder temperature is as follows:
Machine barrel: 260 ℃, 265 ℃, 270 ℃, 260 ℃, 265 ℃, 265 ℃; Adapter temperature: 265 ℃;
The mouth mould: 255 ℃, 245 ℃=die lip temperature; Bowl temperature: cylinder 1 is 30 ℃, and cylinder 2 is 40 ℃, and cylinder 3 is 55 ℃.
The sheet material density of producing is 0.85g/cm
3Its tensile property and dimensional stability see Table 3,4.
Table 3 sheet material tensile property
Table 4 sheets of sizes velocity of variation
Prepared foaming PET sheet material is applicable to makes food trays, electronics pallet.
The preparation of embodiment eight foaming PET sheet materials
The drying of the bottle level PET of IV value 0.95: 175 ℃ of air themperature, time of drying 5～6h, minimum airshed 0.7m
3/ h per kilogram resin.The frothing aid that embodiment four prepares is more than 110 ℃ of dry 2h.
The mixture that in 100 parts of above-mentioned PET, adds the good frothing aid of 10 parts of dryings and 0.1 part of whipping agent supercarbonate and citric acid, the PET melt (being heated to 185 ℃) that will be full of gas then is transported to the extrusion neck ring mold place extrusion moulding of single screw rod sheet extruder, extrusion moulding by the following method:
-extrude line: use single screw rod PET forcing machine, metering of band whipping agent and drying plant.
-forcing machine, mouthful mould and three rod cylinders: identical with common PET sheet production equipment.
Extruder temperature is as follows:
Machine barrel: 260 ℃, 265 ℃, 270 ℃, 260 ℃, 265 ℃, 265 ℃; Adapter temperature: 265 ℃;
The mouth mould: 255 ℃, 245 ℃=die lip temperature; Bowl temperature: cylinder 1 is 30 ℃, and cylinder 2 is 40 ℃, and cylinder 3 is 55 ℃.
The sheet material density of producing is 0.70g/cm
3Its tensile property sees Table 5.
Table 5 sheet material tensile property
Prepared foaming PET sheet material through heater heats to 120 ℃, further after the processing (die-cut, pile), can be made food, medicine and electronic product pallet with plastics suction mould thermoforming, cooling back.Concrete work flow as shown in Figure 2.The scrap stock of receiving in a large number after die-cut.
The utilization again of embodiment nine foaming PET sheet material scrap stock
Adopt 100 parts of bottle level PETs, IV value 0.95, add embodiment six receive scrap stock, the ratio of scrap stock and virgin material is 50: 50, add 3 parts of AZNP whipping agents and 30 parts of frothing aids (frothing aid that embodiment four prepares is more than 110 ℃ of dry 2h) that drying is good, to be full of of the extrusion neck ring mold place extrusion moulding of the PET melt Conveying of gas then, press the extrusion method extrusion moulding among the embodiment six, can obtain the low 0.70g/cm that reaches of density to single screw rod sheet extruder
3Foaming PET sheet material, the specific nature parameter sees Table 6,7.
The tensile property of table 6 sheet material
| Specification | Tensile strength (Mpa) is horizontal | Tensile strength (Mpa) is vertical | Elongation at break (%) is horizontal | Elongation at break (%) is vertical |
| 0.8mm thick wide 640mm | 19.00 | 25.0 | 175.0 | 390.0 |
The size changing rate of table 7 sheet material
| Specification | Size changing rate is (%) laterally | Size changing rate is (%) vertically |
| 0.8mm thick, wide 640mm | -2.77 | -1.67 |
Preparation-obtained foaming PET sheet material is applicable to makes the electronic product plastic-sucking tray.
Claims (7)
- [claim 1] foaming PET sheet material is characterized in that: it is by 100 parts of bottle level PETs, adds 0.1～40 part of frothing aid and 0.1～10 part of whipping agent mixing, and extrusion moulding obtains; Described frothing aid is that the raw material blending by following weight part is prepared from:0.1 the esters of acrylic acid material of～30 parts of ethylene-acrylate-glycidyl methacrylate terpolymers or nucleocapsid structure,0.1～10 parts of high reactivity polyfunctional group materials,10～100 parts of vector resins;Wherein, described vector resin is conjugated polyester resin, PBT resin, polyolefin resin, nylon resin or polycarbonate resin;Described high reactivity polyfunctional group material is at least a in the compound shown in the formula 1～7:
Wherein, R is C1～C8 alkyl.Formula 1
Formula 2
Formula 3
Formula 4
Formula 5
Formula 6
Formula 7. - [claim 2] foaming PET sheet material according to claim 1 is characterized in that: it is by 100 parts of bottle level PETs, adds 0.1～20 part of frothing aid and 0.1～5 part of whipping agent mixing, and extrusion moulding obtains.
- [claim 3] foaming PET sheet material according to claim 1 and 2 is characterized in that: the IV value of described bottle level PET is 0.70～1.40dl/g.
- [claim 4] foaming PET sheet material according to claim 1 and 2 is characterized in that: described whipping agent is AZNP, 5-phenyltetrazole, perhaps supercarbonate and citric acid mixture.
- [claim 5] foaming PET sheet material according to claim 1 and 2 is characterized in that: described vector resin is a kind of in PP resin, Nylon 6, LDPE resin, the PETG resin.
- [claim 6] foaming PET sheet material according to claim 1 and 2 is characterized in that: also be added with toner in the frothing aid.
- [claim 7] prepares the method for the described foaming PET sheet material of claim 1～6, it is characterized in that: may further comprise the steps:A, 0.1～30 part of acrylate multipolymer, 0.1～10 part of high reactivity polyfunctional group material and 10～100 parts of vector resins mix, and extruding pelletization under the melt temperature of vector resin is made frothing aid;B, frothing aid are at the dry 4h of 60 ℃～120oC;C, 100 parts of bottle level PETs add extrusion moulding behind the frothing aid of 0.1～40 part of step B and 0.1～10 part of whipping agent mixing.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1291706B1 (en) * | 1997-05-09 | 1999-01-21 | L M P Impianti S R L | POLYESTER PRODUCTION PROCESS, IN PARTICULAR PET, EXPANDED. |
| WO2000020491A1 (en) * | 1998-10-02 | 2000-04-13 | Djk Techno Science Laboratories Inc. | Foamed polyester resin molding and process for producing the same |
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| CN111607201A (en) * | 2020-05-15 | 2020-09-01 | 浙江恒澜科技有限公司 | Antimony-free green PET (polyethylene terephthalate) foam material for food packaging and preparation method thereof |
| CN111607201B (en) * | 2020-05-15 | 2022-07-08 | 浙江恒逸石化研究院有限公司 | Antimony-free green PET (polyethylene terephthalate) foam material for food packaging and preparation method thereof |
| WO2023065742A1 (en) * | 2021-10-20 | 2023-04-27 | 常州大学 | Blended and filled modified pet foam material and molding method therefor |
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