CN115806728A - Bi-component chain extender master batch for rPET extrusion foaming, and preparation method and application thereof - Google Patents

Bi-component chain extender master batch for rPET extrusion foaming, and preparation method and application thereof Download PDF

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CN115806728A
CN115806728A CN202211565464.8A CN202211565464A CN115806728A CN 115806728 A CN115806728 A CN 115806728A CN 202211565464 A CN202211565464 A CN 202211565464A CN 115806728 A CN115806728 A CN 115806728A
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chain extender
master batch
rpet
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pet
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CN115806728B (en
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陈志强
夏天
常峻峰
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Jiangsu Yuesheng Technology Co ltd
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Abstract

The application discloses a bi-component chain extender master batch for rPET extrusion foaming, and a preparation method and application thereof, wherein the master batch comprises a component A chain extender master batch and a component B chain extender master batch; the component A chain extender master batch is prepared by adopting polyfunctional acid anhydride chain extender and low-melting-point PET copolymer through melt extrusion granulation; wherein the concentration of the anhydride chain extender with polyfunctional group in the master batch of the chain extender A is 10 to 30wt%; the component B chain extender master batch is prepared by melting, extruding and granulating a polyfunctional epoxide chain extender and PET flexibilizer resin; wherein the concentration of the polyfunctional epoxide chain extender in the master batch of the chain extender of the component B is 20 to 50wt%; the chain extender master batch of the component A and the chain extender master batch of the component B are respectively subjected to chain extension and branching reaction with the terminal hydroxyl and the terminal carboxyl of the rPET so as to improve the melt strength and the foaming performance of the rPET and effectively solve the problems of low intrinsic viscosity and high terminal carboxyl concentration of the rPET raw material.

Description

Bi-component chain extender master batch for rPET extrusion foaming and preparation method and application thereof
Technical Field
The application relates to the field of rPET extrusion foaming, in particular to a bi-component chain extender master batch for rPET extrusion foaming and a preparation method and application thereof.
Background
PET foam materials have attracted much attention because of their excellent mechanical strength and temperature resistance and 100% recyclability of uncrosslinked PET, and are widely used as core materials for sandwich structure composite materials instead of PVC foam and Balsa wood. In addition, in the field of home decoration, the foamed PET can replace a solid sheet material so as to save materials and reduce cost. The foamed PET can also be used for automotive interiors, such as automobile roofs, hatracks and the like. PET raw materials are generally linear molecular chain structures and have low molecular weights, low melt strength and melt elasticity. During the foaming process, the cells are easy to break and merge. Therefore, it is necessary to increase the molecular weight of PET by reacting with a chain extender and to introduce a long-chain branched structure to improve the melt strength and foaming property of PET.
In addition, in recent years, carbon emission control has become an important issue of international social concern in order to alleviate the greenhouse effect and improve the ecological environment. According to the American society for Plastic recycling, CO is reported in the production process of 1kg virgin PET (virgin PET, abbreviated as vPET) 2 The emission is 2.23kg, while only 0.91kg of CO is needed to be emitted when 1kg of recycled PET (rPET for short) is produced 2 . Therefore, the rPET used as the extrusion foaming raw material has important environmental significance and can make contributions to the targets of 'carbon peak reaching' and 'carbon neutralization' in China.
Compared to vPET, rPET is generally complex in origin, being different types of bottle grade PET, such as water bottles, oil bottles, carbonated beverage bottles, and different grades of PET, such as mixtures of bottle grade, fiber grade. The types and contents of impurities contained in PET recovered by different routes are also different. In addition, the rPET raw material on the market is complex in form, and can be bottle flakes subjected to cleaning, crushing and drying, granules subjected to extrusion granulation or granules subjected to solid-phase polycondensation. This results in the complicated physical properties of the rPET raw material, such as large differences in molecular weight, end group concentration, comonomer, etc., which poses a great challenge to the PET extrusion foaming process and the stability of material properties.
The existing chain extender master batch technology for PET extrusion foaming is mainly developed based on vPET raw materials and popularized to rPET, and the raw materials of the rPET and the technical characteristics of extrusion foaming of the rPET cannot be designed in a targeted manner. For example, EP 2343330 discloses a chain extender masterbatch for PET extrusion foaming, which uses polyolefin (such as LDPE) and polyester powder as polymer carriers, and pyromellitic dianhydride (PMDA) as a chain extender. However, when the method is popularized and applied to the rPET extrusion foaming process, the PMDA serving as a hydroxyl addition type chain extender cannot perform chain extension reaction with the terminal carboxyl of the rPET and cannot well adjust the foaming process when the properties of the raw material rPET fluctuate because the rPET has the characteristics of non-uniform properties such as intrinsic viscosity, terminal group concentration and the like and high terminal carboxyl group concentration. The preparation of the master batch relates to the grinding of polyester, and the process is complex; in addition, polyolefin LDPE can undergo significant thermal degradation at PET extrusion processing temperatures and is incompatible with PET, affecting the stability of the foaming process and the properties of the final product.
Disclosure of Invention
Based on the defects, the application provides the bi-component chain extender master batch for rPET extrusion foaming and the preparation method and the application thereof, the bi-component chain extender is utilized to respectively carry out chain extension and branching reaction with terminal hydroxyl and terminal carboxyl of the rPET, so that the melt strength and the foaming performance of the rPET are improved, and the problems of low intrinsic viscosity and high terminal carboxyl concentration of the rPET raw material are effectively solved; the application provides a preparation method of the chain extender master batch, the process is simple, and the prepared chain extender master batch is uniform and stable in property; the application provides application of chain extender master batch, which can be used for preparing foamed rPET products.
In a first aspect, the application provides a bicomponent chain extender master batch for rPET extrusion foaming, which adopts the following technical scheme:
a bi-component chain extender master batch for rPET extrusion foaming comprises a component A chain extender master batch and a component B chain extender master batch;
the component A chain extender master batch is prepared by adopting a polyfunctional acid anhydride chain extender and a low-melting-point PET copolymer through melt extrusion granulation; wherein the concentration of the polyfunctional acid anhydride chain extender in the chain extender master batch of the component A is 10 to 30 weight percent; the melting point of the polyfunctional acid anhydride chain extender is lower than or close to the processing temperature of PET; the melting point of the low-melting-point PET copolymer is 100-180 ℃, and the intrinsic viscosity is 0.6-0.85 dL/g;
the component B chain extender master batch is prepared by melting, extruding and granulating an epoxide chain extender with multiple functional groups and PET flexibilizer resin; wherein the concentration of the polyfunctional epoxide chain extender in the master batch of the chain extender B is 20 to 50 weight percent.
The method adopts bi-component chain extenders, namely anhydride chain extenders and epoxide chain extenders, to respectively prepare a component A chain extender master batch and a component B chain extender master batch, and the two chain extender master batches respectively carry out chain extension and branching reactions with terminal hydroxyl and terminal carboxyl of rPET so as to improve the melt strength and the foaming performance of the rPET and effectively solve the problems of low intrinsic viscosity and high terminal carboxyl concentration of the rPET raw material; when the intrinsic viscosity or the end group concentration of the rPET raw material is changed, the stability of the foaming process and the foamed product can be maintained by flexibly adjusting the use amounts of the component A chain extender master batch and the component B chain extender master batch in the extrusion foaming process.
In the component A, the concentration of the polyfunctional acid anhydride chain extender is 10-30 wt%, and when the concentration of the chain extender is less than 10wt%, the addition amount of the master batch in the foaming process is too high, so that the content of the carrier resin in the foamed rPET product needs to be increased, and the mechanical property of the foamed rPET product is reduced; when the concentration of the chain extender is more than 30wt%, the addition amount of the master batch in the foaming rPET is too low, which is not beneficial to the stable feeding of the chain extender master batch and the dispersion of the chain extender master batch in the rPET matrix.
In the component B chain extender master batch, the concentration of the polyfunctional epoxide chain extender is 20-50 wt%, preferably 25-35 wt%, and when the concentration of the chain extender is less than 20wt%, the addition amount of the component B chain extender master batch in the foaming process is too high, so that the cost of the material is increased; when the concentration of the chain extender is more than 50wt%, the addition amount of the chain extender master batch of the component B in the foaming process is too low, so that the feeding of the chain extender of the component B and the dispersion of the chain extender in an extruder are not facilitated on one hand, and the content of the PET flexibilizer resin is low on the other hand, so that the toughening effect is reduced.
The carrier resin of the chain extender master batch of the component A is selected from a low-melting-point PET copolymer, the melting point is between 100 and 180 ℃, and the intrinsic viscosity is between 0.6 and 0.85dL/g; the reaction activity of the chain extender can be protected in the preparation process of the chain extender master batch, the extrusion temperature can be reduced, the sublimation of the anhydride chain extender is reduced or even avoided, and the effective concentration of the chain extender in the master batch is improved; but also can ensure the dispersion uniformity of the chain extender in the carrier resin in the preparation process of the master batch, and improve the quality of the foamed rPET product and the stability of the subsequent extrusion foaming process. The carrier resin of the chain extender master batch of the component B is selected from PET flexibilizer resin, so that stable physical properties can be maintained under the rPET extrusion foaming process condition, the toughness of the foamed rPET product can be improved, and the performance of the foamed rPET product can be improved.
Preferably, the polyfunctional acid anhydride chain extender is selected from one or a combination of pyromellitic dianhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride.
By adopting the technical scheme, pyromellitic dianhydride, PMDA for short, has the melting point of 286 ℃ and the relative molecular mass of 218;3,3', 4' -benzophenone tetracarboxylic dianhydride, BTDA for short, the melting point is 218-222 ℃, and the relative molecular mass is 322; the melting points of the two are lower than or close to the processing temperature of PET, the two are in a molten state in the extrusion foaming process, and the reaction rate is high; and secondly, the two chain extenders are four-functional group chain extenders, so that a branched structure can be effectively formed, and the melt strength and the foaming performance of the rPET are improved. Wherein, the PMDA is used as a chain extender and has the advantages of low raw material cost and small addition amount.
Preferably, the low melting point PET copolymer is selected from one or any combination of polyethylene terephthalate-isophthalate copolymer, polyethylene terephthalate-phthalate copolymer, polyethylene terephthalate-1, 4-cyclohexane dimethanol ester copolymer and polyethylene terephthalate-2, 2-dimethyl-1, 3-propylene glycol ester copolymer.
By adopting the technical scheme, when the dibasic acid used as the third monomer in the carrier resin is selected from isophthalic acid or phthalic acid, and the dihydric alcohol is selected from 1,4 cyclohexanedimethanol and 2, 2-dimethyl-1, 3-propanediol, the melting point of the prepared copolymer is between 100 and 180 ℃, and the intrinsic viscosity is between 0.6 and 0.85dL/g, so that the reaction between the carrier resin and the chain extender is reduced, and the chain extender is ensured to have higher reactivity.
Preferably, the multifunctional epoxide chain extender is one or a combination of triglycidyl isocyanurate and a styrene-acrylate-glycidyl methacrylate copolymer.
By adopting the technical scheme, the epoxide chain extender with multiple functional groups mainly and quickly reacts with terminal carboxyl of rPET to generate a chain extension and branching structure, triglycidyl isocyanurate (TGIC for short, the melting point is 95-98 ℃, the relative molecular weight is 297, the functionality is 3) and a styrene-acrylate-glycidyl methacrylate copolymer (the glass transition temperature is 54 ℃, the number average molecular weight is 2600, and the average functionality is 9) are selected as epoxide chain extenders, and the triglycidyl isocyanurate and the glycidyl methacrylate copolymer have high reactivity under the condition of PET processing temperature, can react with the terminal carboxyl of a rPET raw material, improve the melt elasticity and strength of a foamed rPET product, and enhance the performance of the foamed rPET product.
In addition, the triglycidyl isocyanurate and the styrene-acrylate-glycidyl methacrylate copolymer are powder and easy to add, so that the cost is low; compared with the styrene-acrylate-glycidyl methacrylate copolymer, the functionality of the styrene-acrylate-glycidyl methacrylate copolymer is higher and reaches 9, and the styrene-acrylate-glycidyl methacrylate copolymer has a better branching effect; moreover, the styrene-acrylate-glycidyl methacrylate copolymer is more friendly to human body and environment.
Preferably, the PET toughening agent resin is one or a combination of ethylene-acrylate-glycidyl methacrylate copolymer and polyolefin elastomer grafted glycidyl methacrylate.
By adopting the technical scheme, the ethylene-acrylate-glycidyl methacrylate copolymer and the polyolefin elastomer grafted glycidyl methacrylate are used as carrier resin, so that the polyethylene terephthalate (PET) has good compatibility with PET, excellent temperature resistance, stable property under the condition of PET processing temperature, and good toughening effect on PET foaming material can be realized by low addition amount. In addition, the PET flexibilizer resin does not react with the epoxide chain extender, and the chain extension reactivity of the epoxide can be protected in the preparation process of the master batch. And the melting point of the PET flexibilizer resin is low, so that the dispersion of the chain extender master batch of the component B in a foaming extruder can be promoted, and the stability of the foaming process and the product is improved.
Preferably, the melt index of the PET toughening agent resin is 6-20 g/10min.
By adopting the technical scheme, the fluidity and the dispersion effect of the PET matrix are improved.
Preferably, the content of glycidyl methacrylate GMA in the PET toughening agent resin is 1-10 wt%.
By adopting the technical scheme, the compatibility of the carrier resin and the PET is improved, so that the toughening effect of the foamed rPET product is improved.
In a second aspect, the application provides a preparation method of a bi-component chain extender master batch for rPET extrusion foaming, which adopts the following technical scheme:
a preparation method of bi-component chain extender master batch for rPET extrusion foaming comprises the following steps: the chain extender master batch of the component A is prepared by melting, blending, extruding and granulating the polyfunctional acid anhydride chain extender and the low-melting point PET copolymer; wherein the blending temperature is higher than the melting point of the low-melting-point PET copolymer by 10-50 ℃ and lower than the melting point of the polyfunctional acid anhydride chain extender by 50-150 ℃; the rotating speed of the screw is 100-200 rpm, and air-cooled pelletizing or hot die face pelletizing is carried out;
the chain extender B is prepared by melting, blending and extruding out the polyfunctional epoxide chain extender in the master batch of the chain extender and PET flexibilizer resin, wherein the blending temperature is 50-150 ℃; the rotating speed of the screw is 200-300 rpm, the granulation is carried out by adopting an underwater granulation process, and the temperature of process water for underwater granulation is 2-20 ℃.
By adopting the technical scheme, in the preparation process of the component A chain extender master batch, the blending temperature needs to be higher than 10-50 ℃ of the melting point of the low-melting-point PET copolymer and lower than 50-150 ℃ of the melting point of the polyfunctional anhydride chain extender, because when the blending temperature is too high, the extrusion temperature in the preparation process of the master batch is close to the sublimation temperature of the anhydride chain extender, so that the loss of the chain extender is caused by sublimation after an extruded material is taken out of a machine head, on one hand, the actual concentration of the chain extender in the master batch is reduced, and on the other hand, the surrounding air quality can also be reduced; when the blending temperature is too low or the intrinsic viscosity of the low-melting-point PET copolymer is too high, the viscosity of the low-melting-point PET copolymer is increased in the extrusion process, so that the chain extender is unevenly dispersed in the carrier resin in the preparation process of the master batch, and the quality of the chain extender master batch and the stability of the subsequent extrusion foaming process are reduced.
In the preparation process of the chain extender master batch of the component B, the blending temperature is between 50 and 150 ℃, the temperature is gradually increased from 50 to 150 ℃ to extrusion, when the blending temperature is too low, the toughening agent resin cannot be well plasticized and melted, and the load of a master batch preparation extruder is high; when the blending temperature is too high, the toughening agent resin has high fluidity, and the epoxy chain extender is not well dispersed in the carrier resin.
Compared with the preparation process of the chain extender master batch of the component A, the screw rotating speed of the preparation process of the chain extender master batch of the component B is higher, because the bulk density of the raw materials of the components B is low, the increase of the screw rotating speed can increase the treatment capacity of an extruder, and promote the dispersion of the epoxide chain extender in the carrier resin.
In addition, in the preparation process of the chain extender master batch of the component A, direct contact with water is avoided by means of air cooling or hot die face granulation of extrudate melt, so as to prevent failure of the anhydride chain extender. In the preparation process of the chain extender master batch of the component B, because the melting point and the hardness of the PET flexibilizer resin as the carrier resin are low, an extrudate melt needs to be produced by a continuous underwater pelletizing process, preferably, water cutting pelletizing is adopted, and the temperature of process water for underwater pelletizing is 2-20 ℃, so that the stability of the underwater pelletizing process and the uniformity of the master batch particle size are improved.
In a third aspect, the present application provides a foamed rPET product prepared from a bicomponent chain extender masterbatch extruded and foamed by rPET, which adopts the following technical scheme:
a foamed rPET product prepared by applying rPET extrusion foamed bi-component chain extender master batch comprises any one of a foamed rPET sheet, a foamed rPET plate, a foamed rPET bead and a foamed rPET profiled bar, wherein the addition amount of the chain extender master batch in the preparation of the foamed rPET product is 1-6 wt%.
By adopting the technical scheme, when the intrinsic viscosity or the end group concentration of the rPET raw material is changed, the amounts of the component A chain extender master batch and the component B chain extender master batch in the extrusion foaming process can be flexibly adjusted, so that the stability of the foaming process and the foamed rPET product can be maintained, and the series of foamed rPET products can be prepared into sheets, plates, beads or profiled bars.
In summary, the present application has at least the following technical effects:
1. the method adopts bi-component chain extenders, namely anhydride chain extenders and epoxide chain extenders, to respectively prepare a component A chain extender master batch and a component B chain extender master batch, and the two chain extender master batches respectively carry out chain extension and branching reactions with terminal hydroxyl and terminal carboxyl of rPET so as to improve the melt strength and the foaming performance of the rPET and effectively solve the problems of low intrinsic viscosity and high terminal carboxyl concentration of the rPET raw material; when the intrinsic viscosity or the end group concentration of the rPET raw material is changed, the stability of the foaming process and the foamed product can be maintained by flexibly adjusting the using amounts of the component A chain extender master batch and the component B chain extender master batch in the extrusion foaming process;
2. the carrier resin used by the chain extender master batch of the component A adopts a low-melting-point PET copolymer, the melting point is between 100 and 180 ℃, the intrinsic viscosity is between 0.6 and 0.85dL/g, the reactivity of the chain extender can be protected in the preparation process of the chain extender master batch, the extrusion temperature can be reduced, the sublimation of the anhydride chain extender can be reduced or even avoided, and the effective concentration of the chain extender in the master batch can be improved; the dispersion uniformity of the chain extender in the carrier resin can be ensured in the preparation process of the master batch, and the quality of the foamed rPET product and the stability of the subsequent extrusion foaming process are improved;
3. the carrier resin used by the chain extender master batch of the component B is PET flexibilizer resin, which can not only maintain stable physical properties under rPET extrusion foaming process conditions, but also improve the toughness of foamed rPET products and improve the product performance;
4. the application relates to a bi-component chain extender master batch can be prepared through a one-step method, grinding of carrier resin is not involved, all components are fed from a main feeding port of a double-screw extruder, a side feeding machine is not required to be arranged, other mixing equipment such as an internal mixer and a high-speed mixer is not required, the process is simple, the equipment cost is low, and the prepared chain extender master batch is uniform and stable in product property.
Drawings
Fig. 1 is a schematic diagram of a reaction mechanism of PET with an Epoxy chain extender (Epoxy CE) and an Anhydride chain extender (Anhydride CE).
Fig. 2 is a schematic representation of the change in elastic modulus G' with angular frequency ω of the raw rPET and the foamed rPET sheet of application example 1.
Fig. 3 is an SEM image of the cell morphology of the foamed rPET sheet of application example 1.
Detailed Description
In the existing chain extender master batch technology aiming at extrusion foaming of vPET, only one chain extender is usually adopted, or two or more chain extenders are mixed in a single-component chain extender master batch according to a fixed proportion, and the chain extender master batch can not be effectively adjusted according to the physical property change of rPET in the rPET extrusion foaming process.
In the embodiment of the application, the chain extender master batches with two components, namely the chain extender master batch with the component A and the chain extender master batch with the component B, can respectively perform chain extension and branching reactions with terminal carboxyl and terminal hydroxyl of rPET, so that the molecular weight of the rPET is effectively improved, the molecular weight distribution of the rPET is widened, a long-chain branching structure is introduced into the molecular main chain of the rPET, and the melt strength and the foaming performance of the rPET are obviously improved (the reaction mechanism is shown in figure 1). When the physical properties of the rPET raw material are changed, so that the concentration of the terminal hydroxyl and/or terminal carboxyl is changed, the reactive end group of the rPET can be ensured to fully carry out chain extension and branching reactions by flexibly adjusting the addition amounts of the component A chain extender master batch and the component B chain extender master batch in the extrusion foaming process.
The multifunctional acid anhydride chain extender according to the embodiment of the present invention is one or a combination of pyromellitic dianhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride, preferably pyromellitic dianhydride.
The low melting point PET copolymer according to the embodiment of the present application is one or any combination of a polyethylene terephthalate-isophthalate copolymer, a polyethylene terephthalate-phthalate copolymer, a polyethylene terephthalate-1, 4-cyclohexanedimethanol copolymer, and a polyethylene terephthalate-2, 2-dimethyl-1, 3-propanediol copolymer, and is preferably a polyethylene terephthalate-isophthalate copolymer. The melting point of the low-melting-point PET copolymer is 100-180 ℃, and preferably 100-140 ℃; the intrinsic viscosity is 0.6 to 0.85dL/g, preferably 0.65 to 0.75dL/g.
The component A chain extender masterbatch related to the embodiment of the application is prepared by directly extruding and mixing the components through a double-screw extruder. The temperature of blending is generally 10-50 ℃ higher than the melting point of the PET copolymer, preferably 20-30 ℃ higher than the melting point of the PET copolymer, and 50-150 ℃ lower than the melting point of the anhydride chain extender, preferably 120-150 ℃ lower than the melting point of the chain extender.
The extrusion temperature of the component A chain extender master batch related to the embodiment of the application is generally 100-200 ℃, and preferably 100-150 ℃; all the components are fed from a main feeding port of the double-screw extruder, subjected to processes of melting plasticization, distribution, dispersion, mixing and the like, and then extruded through a porous head. The twin-screw extruder has a length to diameter ratio of 30 to 48, preferably 30 to 36. The screw speed of the extruder is 100 to 200rpm, preferably 150 to 200rpm. And conveying the extrudate melt into a granulator through air cooling, or adopting a hot die surface granulating mode. In the component A chain extender master batch, the concentration of the polyfunctional acid anhydride chain extender is 10 to 30 weight percent, and preferably 15 to 20 weight percent.
The multifunctional epoxide chain extender related to the embodiment of the application adopts one or a combination of triglycidyl isocyanurate and styrene-acrylate-glycidyl methacrylate copolymer; styrene-acrylate-glycidyl methacrylate copolymers are preferably used.
Embodiments of the present disclosure relate to PET toughener resins that employ a combination of one or both of an ethylene-acrylate-glycidyl methacrylate copolymer and a polyolefin elastomer grafted glycidyl methacrylate. The melt index of the PET flexibilizer resin is 6-20 g/10min (190 ℃/2.16 kg); preferably 6 to 12g/10min (190 ℃/2.16 kg). The content of glycidyl methacrylate GMA in the PET flexibilizer resin is 1-10 wt%; preferably 2 to 6wt%.
The component B chain extender master batch related to the embodiment of the application adopts a double-screw extruder to melt and mix all the components, and directly extrudes the mixture to prepare the chain extender master batch, wherein the blending temperature is 50-150 ℃, and preferably 60-120 ℃. Similarly, all the components are fed from a main feeding port of the double-screw extruder, subjected to processes of melting plasticization, distribution, dispersion mixing and the like, and then extruded through a porous head. The double screw extruder is the same as the preparation component A chain extender master batch, and the length-diameter ratio is 30-48, preferably 30-36; the screw speed of the extruder is 200 to 400rpm, preferably 200 to 300rpm. And (3) producing the chain extender master batch of the component B by adopting a continuous underwater granulating process, wherein the temperature of process water for underwater granulating is 2-20 ℃, and preferably 5-10 ℃. The concentration of the epoxide chain extender in the masterbatch of the chain extender of component B is 20 to 50wt%, preferably 25 to 35wt%.
Other processing aids such as heat stabilizers, nucleating agents, flame retardants and the like can also be added into the chain extender masterbatch related to the embodiment of the application. Common flame retardants for polyesters include halogens, phosphorus compounds, and inorganic compounds. Typical foaming nucleating agents comprise calcium powder, talcum powder, nano clay and SiO 2 And the like.
In the rPET extrusion foaming technique, the intrinsic viscosity of rPET is generally 0.6 to 0.85dL/g (test standard GB/T14190, solvent phenol: tetrachloroethane =1, 1w/w, test temperature 25 ℃. + -. 0.1 ℃). As the intrinsic viscosity of rPET decreases, the total end group concentration increases. Wherein the concentration of the terminal carboxyl is usually 20-55 mol/T (the test standard GB/T14190 is measured by a solution titration method by taking potassium hydroxide-ethanol as a solvent and bromophenol blue as an indicator). The intrinsic viscosity and end group concentration of rPET are related to the nature of the PET starting material, as well as the thermal, mechanical history of the primary processing and recycling process.
In the rPET extrusion foaming process related to the application, the rPET raw material can be recycled bottle flakes, and also can be rPET particles, and is used for extrusion foaming after crystallization and drying.
The addition amount of the chain extender master batch of the component A and the chain extender master batch of the component B prepared in the application in the rPET extrusion foaming process is 1-6 wt%, preferably 1.5-3 wt%.
Supercritical fluids such as N can be employed in rPET extrusion foaming processes to which the present application relates 2 、CO 2 Alkanes such as butane, pentane, and the like, and mixtures of two or more of the foregoing blowing agents as physical blowing agents.
The rPET extrusion foaming process related by the application can adopt all forms of extrusion foaming machine sets, such as single-screw extruders, double-screw extruders and series-connected extruder sets (the upper stage is the double-screw extruder/the lower stage is the single-screw extruder, and the upper stage and the lower stage are both single-screw extruders), and the like, and the extrusion foaming rPET products can be sheets, plates, beads, profiles and the like by changing the machine heads of the foaming extruders and the downstream auxiliary machines of the foaming machine sets. In addition, the chain extender master batch related to the application can also be used for the extrusion foaming process of other PET raw materials, such as vPET, PET flame-retardant chips, PET copolymers, such as PETG, and mixtures of different PET raw materials, and can also be used for other high-melting-point polyesters (the melting point is more than or equal to 220 ℃), such as polybutylene terephthalate (PBT), and the like.
The present application will be described in further detail with reference to the following examples and the accompanying drawings.
Example 1:
a bi-component chain extender master batch for rPET extrusion foaming comprises a component A chain extender master batch and a component B chain extender master batch, wherein the preparation method of the component A chain extender master batch comprises the following steps: PMDA is selected as a chain extender, and the concentration of the PMDA in the master batch is 20wt%; the Shanghai petrochemical polyethylene terephthalate-isophthalate copolymer slice is used as carrier resin, the melting point is 120 ℃, the intrinsic viscosity is 0.675dL/g, and the concentration in the master batch is 80wt%. And (3) preparing the master batch, wherein the length-diameter ratio L/D of the double-screw extruder is =48, the screw rotating speed is 150rpm, the blending temperature is 120-165 ℃, and the extrudate melt is subjected to air cooling and then is used for granulating to prepare the chain extender master batch.
The preparation method of the chain extender master batch of the component B comprises the following steps: styrene-methyl methacrylate-glycidyl methacrylate copolymer BASF Joncryl ADR-4368 is selected as a chain extender, the average functionality is 9, and the concentration in the master batch is 30wt%; the thermoplastic polyolefin elastomer grafted glycidyl methacrylate is used as carrier resin, the content of the glycidyl methacrylate is 2-3 wt%, and the melt index is 6g/10min (190 ℃/2.16 kg). The length-diameter ratio L/D =48 of the double-screw extruder for preparing the master batch, the rotating speed of the screw is 200rpm, the blending temperature is 50-100 ℃, the chain extender master batch is prepared by underwater granulating the extrudate melt, and the temperature of the process water for underwater granulating is 10 ℃.
Example 2:
the difference between the bicomponent chain extender master batch for rPET extrusion foaming and the embodiment 1 is that the concentration of the chain extender in the component A chain extender master batch is 10wt%, the concentration of the carrier resin in the master batch is 90wt%, and the component B chain extender master batch is consistent with the embodiment 1.
Example 3:
the difference between the bicomponent chain extender master batch for rPET extrusion foaming and the embodiment 1 is that the concentration of the chain extender in the component A chain extender master batch is 30wt%, the concentration of the carrier resin in the master batch is 70wt%, and the component B chain extender master batch is consistent with the embodiment 1.
Example 4:
the difference between the bicomponent chain extender master batch for rPET extrusion foaming and the embodiment 1 is that the concentration of the chain extender in the chain extender master batch of the component B is 20wt%, the concentration of the carrier resin in the master batch is 80wt%, and the chain extender master batch of the component A is consistent with the embodiment 1.
Example 5:
the difference between the bicomponent chain extender master batch for rPET extrusion foaming and the embodiment 1 is that the concentration of the chain extender in the chain extender master batch of the component B is 50wt%, the concentration of the carrier resin in the master batch is 50wt%, and the chain extender master batch of the component A is consistent with the embodiment 1.
Example 6:
a bi-component chain extender master batch for rPET extrusion foaming is different from the master batch of the chain extender of the component B in the preparation method that: triglycidyl isocyanurate TGIC is selected as a chain extender, the functionality of the chain extender is 3, and the concentration of the chain extender in master batch is 20wt%; styrene-methyl methacrylate-glycidyl methacrylate copolymer is selected as carrier resin, the content of glycidyl methacrylate is 6wt%, and the melt index is 12g/10min (190 ℃/2.16 kg). The length-diameter ratio L/D =48 of the double-screw extruder for preparing the master batch, the rotating speed of the screw is 300rpm, the blending temperature is 50-150 ℃, the chain extender master batch is prepared by underwater granulating the extrudate melt, and the temperature of the process water for underwater granulating is 5 ℃. The component a chain extender masterbatch remains the same as in example 1.
Example 7:
a bicomponent chain extender master batch for rPET extrusion foaming is different from the component A chain extender master batch in the embodiment 1, and the preparation method is as follows: selecting BTDA as a chain extender, wherein the concentration of the BTDA in the master batch is 25wt%; the PET-1, 4-cyclohexanedimethanol ester copolymer chips obtained by characterization of chemical fibers are used as carrier resin, the melting point of the PET-1, 4-cyclohexanedimethanol ester copolymer chips is 115 ℃, the intrinsic viscosity of the PET-1, 4-cyclohexanedimethanol ester copolymer chips is 0.734dL/g, and the concentration of the PET-1, 4-cyclohexanedimethanol ester copolymer chips in master batches is 75wt%. Preparing a master batch, namely preparing chain extender master batch by cooling an extrudate melt by air and then using the cooled extrudate melt for granulating, wherein the length-diameter ratio L/D =44 of a double-screw extruder, the screw rotating speed is 100rpm, and the blending temperature is 100-155 ℃; the component B chain extender masterbatch remained consistent with example 1.
Example 8:
a bicomponent chain extender master batch for rPET extrusion foaming, which is different from the master batch of the component B chain extender in the embodiment 7, and the preparation method is as follows: triglycidyl isocyanurate TGIC is selected as a chain extender, the functionality of the chain extender is 3, and the concentration of the chain extender in the master batch is 20wt%; styrene-methyl methacrylate-glycidyl methacrylate copolymer is selected as carrier resin, the content of glycidyl methacrylate is 6wt%, and the melt index is 12g/10min (190 ℃/2.16 kg). The length-diameter ratio L/D =48 of the double-screw extruder for preparing the master batch, the rotating speed of the screw is 300rpm, the blending temperature is 50-150 ℃, the chain extender master batch is prepared by underwater granulating the extrudate melt, and the temperature of the process water for underwater granulating is 5 ℃.
Application example 1:
a preparation method of the foamed rPET sheet comprises the following steps:
PET extrusion foaming is carried out by adopting a double-screw extruder, the diameter D =75mm of a screw of the extruder, the length-diameter ratio L/D =44, and a static mixer and a porous foaming mould are sequentially arranged at the downstream of the extruder. The porous mold is 620mm wide and 26mm thick. And (4) after the extruded material is discharged from the die, feeding the extruded material into a leveling machine to obtain the foamed PET plate with the rectangular cross section.
The intrinsic viscosity IV of the rPET is =0.78dL/g, the carboxyl end group concentration is 20mol/t, the hydroxyl end group concentration is 60mol/t, the bicomponent chain extender master batch prepared in the embodiment 1 is selected for extrusion foaming, wherein the rPET needs to be dehumidified and dried for 6 hours at the temperature of 160 ℃. The feeding rate of PET was 100kg/hr, the feeding rate of the chain extender master batch of component A was 1.6kg/hr (1.6 wt%), the feeding rate of the chain extender master batch of component B was 2.0kg/hr (2.0 wt%), and the two were fed separately by a weight loss feeder. This example uses isopentane as the blowing agent, which was injected into the extruder via a syringe pump at a rate of 2.1 g/hr. The temperature settings for the extrusion process are shown in the following table:
extrusion section Temperature (. Degree. C.)
Feeding section 60
Melting section 280～285
Reaction section 290～300
Cooling section 250～260
Static mixer 255～260
Die set 260～265
Application example 2:
a foamed rPET sheet, differing from application example 1 in that the masterbatch prepared in example 2 was used as the bicomponent chain extender masterbatch, the feed rate of the chain extender masterbatch of component a was 3.3kg/hr (3.3 wt%), and the feed rate of the chain extender masterbatch of component B was 2.0kg/hr (2.0 wt%).
Application example 3:
a foamed rPET sheet, differing from application example 1 in that the masterbatch prepared in example 3 was used as the bicomponent chain extender masterbatch, the feed rate of the chain extender masterbatch of component a was 1.1kg/hr (1.1 wt%), and the feed rate of the chain extender masterbatch of component B was 2.0kg/hr (2.0 wt%).
Application example 4:
a foamed rPET sheet material is different from application example 1 in that the masterbatch prepared in example 4 is used as the bicomponent chain extender masterbatch, the feeding rate of the component A chain extender masterbatch is 1.6kg/hr (1.6 wt%), and the feeding rate of the component B chain extender masterbatch is 3.0kg/hr (3.0 wt%).
Application example 5:
a foamed rPET sheet material is different from application example 1 in that the master batch prepared in example 5 is adopted as the bi-component chain extender master batch, the feeding rate of the component A chain extender master batch is 1.6kg/hr (1.6 wt%), and the feeding rate of the component B chain extender master batch is 1.2kg/hr (1.2 wt%).
Application example 6:
a foamed rPET sheet material is different from application example 1 in that the master batch prepared in example 6 is adopted as the bi-component chain extender master batch, the feeding rate of the component A chain extender master batch is 1.6kg/hr (1.6 wt%), and the feeding rate of the component B chain extender master batch is 1.5kg/hr (1.5 wt%).
Application example 7:
a foamed rPET sheet, differing from application example 1 in that the masterbatch prepared in example 7 was used as the bicomponent chain extender masterbatch, the feed rate of the chain extender masterbatch of component a was 1.9kg/hr (1.9 wt%), and the feed rate of the chain extender masterbatch of component B was 2.0kg/hr (2.0 wt%).
Application example 8:
a foamed rPET sheet, differing from application example 1 in that the bicomponent chain extender masterbatch obtained in example 8 was used, the feed rate of the component a chain extender masterbatch was 1.9kg/hr (1.9 wt%), and the feed rate of the component B chain extender masterbatch was 2.2kg/hr (2.2 wt%).
Application example 9:
a foamed rPET sheet, which is different from application example 1 in that: the limiting viscosity of rPET is 0.65dL/g, the terminal carboxyl group concentration is 40mol/t, the terminal hydroxyl group concentration is 64mol/t, the feeding rate of the chain extender master batch of the component A is 1.7kg/hr (1.7 wt%), and the feeding rate of the chain extender master batch of the component B is 4.0kg/hr (4.0 wt%).
Application example 10:
a foamed rPET sheet, which is different from application example 1 in that: the limiting viscosity of rPET is 0.70dL/g, the terminal carboxyl group concentration is 35mol/t, the terminal hydroxyl group concentration is 58mol/t, the feeding rate of the component A chain extender master batch is 1.6kg/hr (1.6 wt%), and the feeding rate of the component B chain extender master batch is 3.5kg/hr (3.5 wt%).
Application example 11:
a foamed rPET sheet, which is different from application example 1 in that: the limiting viscosity of rPET is 0.85dL/g, the terminal carboxyl group concentration is 20mol/t, the terminal hydroxyl group concentration is 50mol/t, the feeding rate of the component A chain extender master batch is 1.4kg/hr (1.4 wt%), and the feeding rate of the component B chain extender master batch is 2.0kg/hr (2.0 wt%).
Application example 12:
a preparation method of the foamed rPET sheet material comprises the following steps:
and (3) carrying out PET (polyethylene terephthalate) extrusion foaming by adopting a series-connected extruder unit, wherein the screw diameter D =95mm and the length-diameter ratio L/D =40 of an upper-stage double-screw extruder, the diameter D =250mm and the length-diameter ratio L/D =30 of a lower-stage single-screw extruder. And a static mixer and a porous foaming mould are sequentially arranged at the downstream of the extruder. The porous mold has a width of 1200mm and a thickness of 60mm. And (4) after the extruded material is discharged from the die, feeding the extruded material into a leveling machine to obtain the foamed PET plate with the rectangular cross section.
The intrinsic viscosity IV of the rPET used is =0.82dL/g, the carboxyl end group concentration is 20mol/t, the hydroxyl end group concentration is 54mol/t, the bicomponent chain extender master batch prepared in the embodiment 8 is selected for extrusion foaming, wherein the rPET needs to be dehumidified and dried for 6 hours at the temperature of 160 ℃. The feeding rate of PET was 500kg/hr, the feeding rate of the chain extender master batch of component A was 8.7kg/hr (1.74 wt%), the feeding rate of the chain extender master batch of component B was 5kg/hr (1 wt%), and both were fed separately by a weight loss feeder.
This example uses supercritical CO 2 As the foaming agent, the foaming agent was injected into the extruder through a syringe pump at a rate of 3.5 kg/hr. The temperature settings for the extrusion process are shown in the following table:
Figure BDA0003986441920000141
application example 13:
a foamed rPET sheet, which is different from application example 12 in that: the limiting viscosity of rPET is 0.73dL/g, the terminal carboxyl group concentration is 40mol/t, the terminal hydroxyl group concentration is 48mol/t, the feeding rate of the chain extender master batch of the component A is 7.75kg/hr (1.55 wt%), and the feeding rate of the chain extender master batch of the component B is 9.9kg/hr (1.98 wt%).
Application example 14:
a foamed rPET sheet is different from the application example 12 in that the intrinsic viscosity of rPET is 0.68dL/g, the carboxyl end group concentration is 45mol/t, the hydroxyl end group concentration is 52mol/t, the feeding rate of a chain extender master batch of the component A is 8.4kg/hr (1.68 wt%), and the feeding rate of a chain extender master batch of the component B is 11kg/hr (2.2 wt%).
Comparative example 1:
a foamed rPET sheet material is different from an application example 1 in that a master batch of a bi-component chain extender selects a polyethylene terephthalate-isophthalate copolymer slice of Shanghai petrochemical industry as a carrier resin, the melting point is 120 ℃, the intrinsic viscosity is 0.675dL/g, two chain extenders select PMDA and a styrene-acrylate-glycidyl methacrylate copolymer (BASF Joncryl ADR-4368), the concentration of PMDA in the master batch is 20%, the concentration of the styrene-acrylate-glycidyl methacrylate copolymer (BASF Joncryl ADR-4368) in the master batch is 30%, and the concentration of the carrier resin in the master batch is 50%; and preparing the master batch by using a double-screw extruder, wherein the length-diameter ratio L/D =48, the rotating speed of a screw is 150rpm, the blending temperature is 120-165 ℃, and an extrudate melt is air-cooled and then used for granulating to prepare the chain extender master batch. The used recycled rPET raw material is the same as the application example 1, and the addition amount of the bi-component chain extender master batch is 3.6wt%.
Comparative example 2:
a foamed rPET sheet is different from application example 1 in that a double-component chain extender master batch selects polyethylene terephthalate-isophthalate copolymer slices of Shanghai petrochemical industry as carrier resin, the melting point is 120 ℃, the intrinsic viscosity is 0.675dL/g, two chain extenders select PMDA and BTDA, the concentration of PMDA in the master batch is 20%, the concentration of BTDA in the master batch is 30%, and the concentration of the carrier resin in the master batch is 50%; and (3) preparing the master batch, wherein the length-diameter ratio L/D of the double-screw extruder is =48, the screw rotating speed is 150rpm, the blending temperature is 120-165 ℃, and the extrudate melt is subjected to air cooling and then is used for granulating to prepare the chain extender master batch. The used recycled rPET raw material is the same as the application example 1, and the addition amount of the bi-component chain extender master batch is 3.6wt%.
Comparative example 3:
a foamed rPET sheet is different from application example 1 in that the concentrations of chain extenders in a bi-component chain extender master batch are different, the concentration of a component A chain extender in the component A chain extender master batch is 5wt%, and the concentration of a component B chain extender in the component B chain extender master batch is 10wt%; the recycled rPET raw material is the same as the application example 1, and the addition amount of the bi-component chain extender master batch is 3.6wt%.
Comparative example 4:
a foamed rPET sheet is different from application example 1 in that the concentrations of chain extenders in a bi-component chain extender master batch are different, the concentration of a component A chain extender in the component A chain extender master batch is 40wt%, and the concentration of a component B chain extender in the component B chain extender master batch is 60wt%; the recycled rPET raw material is the same as the application example 1, and the addition amount of the bi-component chain extender master batch is 3.6wt%.
The mechanical property detection is carried out on the foamed rPET plates prepared according to the application examples and the comparative examples, and the detection standards and the detection results are shown in the following table:
Figure BDA0003986441920000151
Figure BDA0003986441920000161
Figure BDA0003986441920000171
according to the application examples 1, 6-8, the comparative examples 1-2 and the detection results shown in the table, the method adopts the bi-component chain extender master batch, the component A chain extender master batch adopts the anhydride chain extender, the component B chain extender master batch adopts the epoxide chain extender, and the two chain extenders respectively carry out chain extension and branching reaction with the terminal hydroxyl and the terminal carboxyl of rPET, so that the melt strength and the foaming performance of the rPET are improved, and the preparation of the foamed rPET plate with excellent mechanical properties is realized. The two-component chain extender master batch of the comparative examples 1-2 is prepared by mixing two chain extenders in a fixed ratio, and when the intrinsic viscosity or the end group concentration of the recycled rPET raw material changes, the end group of the recycled rPET raw material has the condition of insufficient reaction, so that the foaming process is insufficient and the mechanical property of the foamed rPET plate is reduced. In addition, compared with comparative examples 1-2, in the component B chain extender master batch, when the PET flexibilizer resin is adopted as the carrier resin, the shear elongation at break of the prepared foamed rPET sheet is higher.
Referring to fig. 2, it can be seen that the elastic modulus of the foamed rPET is greatly improved compared with that of the raw material rPET after the chain extension and branching reaction of the foamed rPET with the bicomponent chain extender master batch, which indicates that the molecular weight of the rPET after the chain extension reaction is increased, and the expanded rPET has wide molecular weight distribution and a long chain branching structure. Referring to fig. 3, it can be known that in the foamed rPET sheet prepared in application example 1, the rPET cells have good morphology, uniform size and high closed cell rate.
According to the application examples 1-5, the comparative examples 3-4 and the detection results in the table, when the concentrations of the two chain extenders in the master batch are different, the addition amount of the master batch of the two chain extenders is adjusted in real time, so that the prepared foamed rPET plate has excellent mechanical properties; in the comparative example 3, when the concentrations of the two chain extenders are too low, when the same amount of the chain extender master batch of the component A as that in the application example 1 is added, the foaming process is insufficient, and the mechanical property of the foamed rPET plate can be influenced; in comparative example 4, when the master batches of the two chain extenders were too high, the addition of the master batches during the foaming process was too low, which was not conducive to dispersion of the chain extender master batches in the rPET matrix, significantly reducing the mechanical properties of the foamed rPET panels.
According to the detection results of the application example 1, the application examples 9-14 and the table above, the bi-component chain extender master batch is used for recovering rPET during extrusion foaming, when the intrinsic viscosity or the end group concentration of the rPET raw material is changed, the concentration of the chain extender in the master batch is combined, the use amounts of the component A chain extender master batch and the component B chain extender master batch in the extrusion foaming process can be flexibly adjusted, the stability of the foaming process and the foamed product is maintained, and the foamed rPET plate with excellent comprehensive mechanical properties is prepared.

Claims (9)

1. A bi-component chain extender master batch for rPET extrusion foaming is characterized in that: the master batch comprises a component A chain extender master batch and a component B chain extender master batch;
the component A chain extender master batch is prepared by melting, extruding and granulating a polyfunctional acid anhydride chain extender and a low-melting point PET copolymer; wherein the concentration of the anhydride chain extender with polyfunctional group in the master batch of the chain extender A is 10 to 30wt%; the melting point of the anhydride chain extender with the polyfunctional group is lower than or close to the processing temperature of PET; the low-melting-point PET copolymer has a melting point of 100 to 180 ℃ and an intrinsic viscosity of 0.6 to 0.85dL/g;
the component B chain extender master batch is prepared by melting, extruding and granulating an epoxide chain extender with multiple functional groups and PET flexibilizer resin; wherein the concentration of the polyfunctional epoxide chain extender in the master batch of the chain extender of the component B is 20 to 50wt%.
2. The bicomponent chain extender masterbatch for rPET extrusion foaming according to claim 1, wherein: the anhydride chain extender with multiple functional groups is one or a combination of pyromellitic dianhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride.
3. The bicomponent chain extender masterbatch for rPET extrusion foaming according to claim 2, wherein: the low-melting-point PET copolymer is one or any combination of a polyethylene terephthalate-isophthalate copolymer, a polyethylene terephthalate-phthalate copolymer, a polyethylene terephthalate-1, 4 cyclohexane dimethanol ester copolymer and a polyethylene terephthalate-2, 2-dimethyl-1, 3-propylene glycol ester copolymer.
4. The bicomponent chain extender masterbatch for rPET extrusion foaming according to claim 1, wherein: the polyfunctional epoxide chain extender is one or a combination of triglycidyl isocyanurate and a styrene-acrylate-glycidyl methacrylate copolymer.
5. The bicomponent chain extender masterbatch for rPET extrusion foaming according to claim 4, wherein: the PET toughening agent resin is one or a composition of ethylene-acrylate-glycidyl methacrylate copolymer and polyolefin elastomer grafted glycidyl methacrylate.
6. The bicomponent chain extender masterbatch for rPET extrusion foaming according to claim 5, wherein: the melt index of the PET flexibilizer resin is 6-20g/10 min.
7. The bicomponent chain extender masterbatch for rPET extrusion foaming according to claim 5, wherein: the content of glycidyl methacrylate GMA in the PET flexibilizer resin is 1-10wt%.
8. The preparation method of the bicomponent chain extender masterbatch for rPET extrusion foaming as claimed in any one of claims 1 to 7, which comprises the following steps:
the chain extender with polyfunctional group in the chain extender master batch of the component A and the PET copolymer with low melting point are prepared by melt blending, extrusion and granulation; wherein the blending temperature is higher than the melting point of the low-melting-point PET copolymer by 10 to 50 ℃ and lower than the melting point of the polyfunctional acid anhydride chain extender by 50 to 150 ℃; the rotating speed of the screw is 100 to 200rpm, and air cooling granulation or hot die face granulation is carried out;
the chain extender B is prepared by melting, blending and extruding the polyfunctional epoxide chain extender in the master batch of the chain extender B and PET flexibilizer resin for granulation, wherein the blending temperature is 50-150 ℃; the rotating speed of the screw is 200 to 300rpm, the granulation is carried out by adopting an underwater granulation process, and the process water temperature for underwater granulation is 2 to 20 ℃.
9. The foamed rPET product prepared by applying the bi-component chain extender master batch for rPET extrusion foaming according to any one of claims 1 to 7, is characterized in that: the foamed rPET product comprises any one of a foamed rPET sheet, a foamed rPET bead and a foamed rPET profiled bar, and the addition amount of the bi-component chain extender master batch in the preparation of the foamed rPET product is 1-6 wt%.
CN202211565464.8A 2022-12-07 2022-12-07 Bi-component chain extender master batch for rPET extrusion foaming and preparation method and application thereof Active CN115806728B (en)

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