CN115806728B - 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 PDFInfo
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- CN115806728B CN115806728B CN202211565464.8A CN202211565464A CN115806728B CN 115806728 B CN115806728 B CN 115806728B CN 202211565464 A CN202211565464 A CN 202211565464A CN 115806728 B CN115806728 B CN 115806728B
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Abstract
The application discloses a bi-component chain extender master batch for rPET extrusion foaming, 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 a polyfunctional acid anhydride chain extender and a low-melting-point PET copolymer through melt extrusion granulation; wherein the concentration of the multifunctional anhydride chain extender in the component A chain extender master batch is 10-30wt%; the component B chain extender master batch is prepared by adopting epoxy chain extender with multifunctional groups and PET toughening agent resin to carry out melt extrusion granulation; wherein the concentration of the multifunctional epoxide chain extender in the component B chain extender master batch is 20-50wt%; the component A chain extender master batch and the component B chain extender master batch are respectively subjected to chain extension and branching reaction with hydroxyl ends and carboxyl ends of rPET, so that the melt strength and foaming performance of the rPET are improved, and the problems of low intrinsic viscosity and high carboxyl end concentration of the rPET raw material are effectively solved.
Description
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 are widely paid attention to because of their excellent mechanical strength, temperature resistance and 100% recycling of uncrosslinked PET, and are widely used as core materials for sandwich-structured composite materials instead of PVC foam and Balsa wood. In addition, in the field of home furnishings, the foamed PET can replace solid sheet materials so as to save materials and reduce cost. The foamed PET can also be used for automotive interiors such as automotive roofs, hatracks, and the like. PET feedstock is typically of linear molecular chain structure and low molecular weight, with low melt strength and melt elasticity. In the foaming process, the rupture and the combination of the foam cells are easy to occur. Therefore, it is necessary to increase the molecular weight of PET by reaction with a chain extender, and to introduce a long chain branching structure to increase the melt strength and foaming properties of PET.
In addition, in recent years, carbon emission control has become an important issue of international social concern for alleviating the greenhouse effect and improving the ecological environment. CO in the production of 1kg virgin PET resin (virgin PET, abbreviated as vPET) reported by the American society for plastic recovery 2 The discharge amount was 2.23kg, and only 0.91kg of CO was discharged to produce 1kg of recycled PET resin (rPET for short) 2 . Therefore, the rPET is used as an extrusion foaming raw material, has important environmental significance, and can contribute to the carbon peak and carbon neutralization targets in China.
Compared to vPET, rPET is often of complex origin, being a different kind of bottle grade PET, such as water bottles, oil bottles, carbonated beverage bottles, and a different grade PET, such as a mixture of bottle grade, fiber grade. The types and contents of impurities contained in the PET recovered by different routes are different. In addition, the rPET raw material on the market has a complex form and can be a bottle tablet which is cleaned, crushed and dried, or can be granules which are extruded and granulated or granules which are subjected to solid phase polycondensation. This results in complex physical properties of the rPET raw material, such as large differences in molecular weight, end group concentration, comonomer, etc., which presents a great challenge for the PET extrusion foaming process and stability of material properties.
The existing chain extender master batch technology for PET extrusion foaming is mainly developed based on vPET raw materials and then popularized to rPET, and cannot be specifically designed for the raw materials of rPET and the technical characteristics of extrusion foaming thereof. For example, patent EP 2343330 discloses a chain extender masterbatch for PET extrusion foaming with polyolefin (e.g.LDPE) and polyester powder as polymer carrier and pyromellitic dianhydride (PMDA) as chain extender. However, when the PMDA is popularized and used in the extrusion foaming process of rPET, PMDA serving as a hydroxyl addition type chain extender cannot perform chain extension reaction with the carboxyl end group of rPET because the rPET has the characteristics of uneven properties such as intrinsic viscosity, end group concentration and the like and high carboxyl end group concentration, and the foaming process cannot be well adjusted when the properties of raw material rPET fluctuate. And the masterbatch preparation involves grinding of polyester, and the process is complex; in addition, polyolefin LDPE undergoes significant thermal degradation at the 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 a bi-component chain extender master batch for rPET extrusion foaming, a preparation method and application thereof, wherein the bi-component chain extender is used for carrying out chain extension and branching reaction with hydroxyl end groups and carboxyl end groups of rPET respectively so as to improve the melt strength and foaming performance of rPET, and the problems of low intrinsic viscosity and high carboxyl end group concentration of rPET raw materials are effectively solved; the preparation method of the chain extender master batch is simple in process, and the prepared chain extender master batch is uniform and stable in property; the application provides application of a chain extender master batch, which can be used for preparing a foaming rPET product.
In a first aspect, the present application provides a bicomponent chain extender masterbatch for rPET extrusion foaming, which adopts the following technical scheme:
a bi-component chain extender master batch for rPET extrusion foaming, 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 a polyfunctional acid anhydride chain extender and a low-melting-point PET copolymer through melt extrusion granulation; wherein the concentration of the multifunctional anhydride chain extender in the component A chain extender master batch is 10-30wt%; the melting point of the multifunctional anhydride-based chain extender is lower than or near 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 adopting a multifunctional epoxide chain extender and PET toughening agent resin to carry out melt extrusion granulation; wherein the concentration of the multifunctional epoxide chain extender in the component B chain extender master batch is 20 to 50 weight percent.
The method adopts the bi-component chain extender, namely the anhydride chain extender and the epoxide chain extender, to prepare the component A chain extender master batch and the component B chain extender master batch respectively, and the two chain extender master batches respectively carry out chain extension and branching reaction with hydroxyl ends and carboxyl ends of rPET so as to improve the melt strength and foaming performance of rPET, and effectively solve the problems of low intrinsic viscosity and high carboxyl end concentration of rPET raw materials; when the intrinsic viscosity or end group concentration of rPET raw materials changes, the stability of the foaming process and the foaming product can be maintained by flexibly adjusting the dosage 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 chain extender master batch, the concentration of the multifunctional anhydride chain extender is between 10 and 30 weight percent, when the concentration of the chain extender is less than 10 weight percent, the addition amount of the master batch in the foaming process is too high, the content of carrier resin in a foaming rPET product is required to be improved at the same time, and the mechanical property of the foaming rPET product is reduced; when the concentration of the chain extender is more than 30wt%, the addition amount of the master batch in the foamed rPET is too low, which is unfavorable for stable feeding of the chain extender master batch and dispersion thereof in the rPET matrix.
In the component B chain extender master batch, the concentration of the multifunctional epoxide chain extender is 20-50 wt%, preferably 25-35 wt%, 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 component B chain extender master batch in the foaming process is too low, which is not beneficial to the feeding of the component B chain extender and the dispersion of the component B chain extender in an extruder, and also causes low content of PET toughening agent resin, and reduces the toughening effect.
The carrier resin of the chain extender master batch of the component A selects a low-melting-point PET copolymer, the melting point is 100-180 ℃, and the intrinsic viscosity is 0.6-0.85 dL/g; the method not only can protect the reactivity of the chain extender in the preparation process of the master batch of the chain extender, but also can reduce the extrusion temperature, reduce or even avoid the sublimation of the anhydride chain extender, and improve the effective concentration of the chain extender in the master batch; and the dispersion uniformity of the chain extender in the carrier resin in the masterbatch preparation process can be ensured, and the quality of the foamed rPET product and the stability of the subsequent extrusion foaming process can be improved. The carrier resin of the component B chain extender master batch selects PET toughening agent resin, so that stable physical properties can be maintained under the process condition of rPET extrusion foaming, the toughness of the foamed rPET product can be improved, and the performance of the foamed rPET product can be improved.
Preferably, the multifunctional anhydride chain extender is selected from one or a combination of two of pyromellitic dianhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride.
By adopting the technical scheme, pyromellitic dianhydride, PMDA for short, with a melting point of 286 ℃ and relative molecular mass of 218;3,3', 4' -diphenyl ketone tetracarboxylic dianhydride, BTDA for short, melting point 218-222 ℃ and relative molecular mass 322; the melting points of the two are lower than or approximate to the processing temperature of PET, and the two are in a molten state in the extrusion foaming process, so that the reaction rate is high; secondly, the two chain extenders are tetrafunctional chain extenders, so that a branched structure can be effectively formed, and the melt strength and foaming performance of rPET are improved. Wherein, 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-m-phthalic acid glycol copolymer, polyethylene terephthalate-1, 4-cyclohexanedimethanol ester copolymer and polyethylene terephthalate-2, 2-dimethyl-1, 3-propanediol ester copolymer.
By adopting the technical scheme, when the dibasic acid serving as the third monomer in the carrier resin is isophthalic acid or phthalic acid, and the dibasic alcohol is 1, 4-cyclohexanedimethanol or 2, 2-dimethyl-1, 3-propanediol, the prepared copolymer has a melting point of 100-180 ℃ and an intrinsic viscosity of 0.6-0.85 dL/g, and is favorable for reducing the reaction of the carrier resin and the chain extender, so that the chain extender is ensured to have higher reactivity.
Preferably, the multifunctional epoxide chain extender is one or a combination of triglycidyl isocyanurate and styrene-acrylate-glycidyl methacrylate copolymer.
By adopting the technical scheme, the multifunctional epoxide chain extender mainly reacts with the carboxyl end group 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-acrylic ester-glycidyl methacrylate copolymer (the glass transition temperature is 54 ℃, the number average molecular weight is 2600, and the average functionality is 9) are adopted as the epoxide chain extender, and have high reactivity under the PET processing temperature condition, can react with the carboxyl end group of rPET raw materials, improve the melt elasticity and strength of the foamed rPET product and strengthen the performance of the foamed rPET product.
In addition, the triglycidyl isocyanurate and the styrene-acrylic ester-glycidyl methacrylate copolymer are all powder which is easy to add and has low cost; compared with the two, the functionality of the styrene-acrylic ester-glycidyl methacrylate copolymer is higher and reaches 9, and the branching effect is better; furthermore, 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 two of ethylene-acrylic ester-glycidyl methacrylate copolymer and polyolefin elastomer grafted glycidyl methacrylate.
By adopting the technical scheme, the ethylene-acrylic ester-glycidyl methacrylate copolymer and the polyolefin elastomer grafted glycidyl methacrylate are used as carrier resin, so that the polyethylene terephthalate/polyethylene terephthalate copolymer has good compatibility with PET, has excellent temperature resistance, still keeps stable properties under the condition of PET processing temperature, and can play a good toughening role on PET foaming materials with low addition. In addition, the PET toughening agent resin does not react with the epoxide chain extender, so that the chain extender activity of the epoxide can be protected in the masterbatch preparation process. In addition, the PET toughening agent resin has low melting point, and can promote the dispersion of the component B chain extender master batch in a foaming extruder, thereby improving the foaming process and the stability of products.
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 1-10wt%.
By adopting the technical scheme, the compatibility of the carrier resin and PET is improved, so that the toughening effect of the foamed rPET product is improved.
In a second aspect, the present application provides a method for preparing a bicomponent chain extender masterbatch for rPET extrusion foaming, which adopts the following technical scheme:
the preparation method of the bi-component chain extender master batch for rPET extrusion foaming comprises the following steps: the multifunctional anhydride chain extender in the component A chain extender master batch and the low-melting-point PET copolymer are prepared by melt blending and extrusion granulation; wherein the blending temperature is 10-50 ℃ higher than the melting point of the low-melting PET copolymer and 50-150 ℃ lower than the melting point of the multifunctional anhydride chain extender; the rotating speed of the screw is 100-200 rpm, and the air-cooled granulating or hot die face granulating is carried out;
the multifunctional epoxide chain extender and PET toughening agent resin in the component B chain extender master batch are prepared by melt blending and extrusion granulating, wherein the blending temperature is 50-150 ℃; the rotation speed of the screw is 200-300 rpm, the underwater granulating process is adopted for granulating, and the water temperature of the process water for underwater granulating is 2-20 ℃.
By adopting the technical scheme, in the preparation process of the master batch of the chain extender of the component A, the blending temperature is required to be 10-50 ℃ higher than the melting point of the PET copolymer with low melting point and 50-150 ℃ lower than the melting point of the anhydride chain extender with multifunctional groups, 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 the extrudate exits 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 is also 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 masterbatch preparation process, and the quality of the chain extender masterbatch and the stability of the subsequent extrusion foaming process are reduced.
In the preparation process of the component B chain extender master batch, 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 the master batch preparation extruder is high; when the blending temperature is too high, the toughener resin is high in flowability and the epoxide chain extender is poorly dispersed in the carrier resin.
Compared with the preparation process of the component A chain extender master batch, the screw rotating speed of the preparation process of the component B chain extender master batch is higher, because the bulk density of the raw materials of each component of the component B is low, the processing capacity of an extruder can be increased by increasing the screw rotating speed, and meanwhile, the dispersion of the epoxide chain extender in the carrier resin is promoted.
In addition, in the preparation process of the component A chain extender master batch, the extrudate melt is cut into particles by an air cooling or hot die surface, so that the extrudate melt is prevented from being in direct contact with water, and the failure of the anhydride chain extender is prevented. In the preparation process of the component B chain extender master batch, because the PET toughening agent resin used as the carrier resin has lower melting point and hardness, extrudate melt is produced by a continuous underwater pelletizing process, preferably water is used for cutting and pelletizing, and the water temperature of the process water for underwater pelletizing is 2-20 ℃, thereby being beneficial to improving the stability of the underwater pelletizing process and the uniformity of the size of the master batch.
In a third aspect, the present application provides a foamed rPET product prepared from a bi-component chain extender masterbatch extruded and foamed using rPET, which adopts the following technical scheme:
the foaming rPET product prepared by extruding and foaming bi-component chain extender master batch by using rPET comprises any one of foaming rPET sheet, foaming rPET bead and foaming rPET profiled bar, wherein the addition amount of the chain extender master batch in preparing the foaming rPET product is 1-6wt%.
Through adopting above-mentioned technical scheme, when rPET raw materials intrinsic viscosity or terminal group concentration change, the quantity of component A chain extender masterbatch and component B chain extender masterbatch in the extrusion foaming process can be adjusted in a flexible way, help maintaining the foaming process and the stability of foaming rPET product to prepare the serial products of foaming rPET, can be sheet, panel, bead or profiled bar.
In summary, the present application has at least the following technical effects:
1. the method adopts the bi-component chain extender, namely the anhydride chain extender and the epoxide chain extender, to prepare the component A chain extender master batch and the component B chain extender master batch respectively, and the two chain extender master batches respectively carry out chain extension and branching reaction with hydroxyl ends and carboxyl ends of rPET so as to improve the melt strength and foaming performance of rPET, and effectively solve the problems of low intrinsic viscosity and high carboxyl end concentration of rPET raw materials; when the intrinsic viscosity or end group concentration of rPET raw materials changes, the use amount of the component A chain extender master batch and the use amount of 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 foaming product can be maintained;
2. the carrier resin used for the component A chain extender master batch 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 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 can be reduced or even avoided, and the effective concentration of the chain extender in the master batch can be improved; in the process of preparing the master batch, the dispersion uniformity of the chain extender in the carrier resin can be ensured, and the quality of the foamed rPET product and the stability of the subsequent extrusion foaming process can be improved;
3. the carrier resin used for the component B chain extender master batch adopts PET toughening agent resin, which not only can maintain stable physical properties under the process condition of rPET extrusion foaming, but also can improve the toughness of the foamed rPET product and the product performance;
4. the bi-component chain extender master batch can be prepared by a one-step method, does not relate to grinding of carrier resin, is fed from a main feeding port of a double-screw extruder, does not need a side feeding machine, does not need other mixing equipment such as an internal mixer, a high-speed mixer and the like, is simple in process and low in equipment cost, and the prepared chain extender master batch is uniform and stable in product property.
Drawings
FIG. 1 is a schematic illustration of the reaction mechanism of PET with Epoxy chain extender (Epoxy CE) and Anhydride chain extender (Anhydride CE).
Fig. 2 is a graph showing the change of the elastic modulus G' with the angular frequency ω of the raw material 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 technology of the chain extender master batch aiming at the extrusion foaming of the vPET, only one chain extender is generally adopted, or two or more chain extenders are mixed in a single-component chain extender master batch in a fixed proportion, and the effective adjustment cannot be carried out according to the physical property change of the rPET in the extrusion foaming process of the rPET.
According to the embodiment of the application, the bi-component chain extender master batch, namely the component A chain extender master batch and the component B chain extender master batch, can respectively carry out chain extension and branching reaction with the carboxyl end and the hydroxyl end of rPET, so that the molecular weight of rPET is effectively improved, the molecular weight distribution of rPET is widened, a long chain branching structure is introduced into the molecular main chain of rPET, and the melt strength and the foaming performance of rPET are obviously improved (the reaction mechanism is shown in figure 1). When the physical properties of the rPET raw material change and the concentration of hydroxyl and/or carboxyl ends changes, the chain extension and branching reaction of the reactive end group of the rPET can be ensured by flexibly adjusting the addition amount of the component A chain extender master batch and the component B chain extender master batch in the extrusion foaming process.
The polyfunctional acid anhydride-based chain extender according to the embodiment of the present application is a composition comprising one or both 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 preferably a polyethylene terephthalate-isophthalate copolymer, a polyethylene terephthalate-phthalate copolymer, a polyethylene terephthalate-1, 4-cyclohexanedimethanol copolymer, or a polyethylene terephthalate-2, 2-dimethyl-1, 3-propanediol copolymer. The melting point of the low melting point PET copolymer is 100-180 ℃, preferably 100-140 ℃; the intrinsic viscosity is 0.6-0.85 dL/g, preferably 0.65-0.75 dL/g.
The component A chain extender master batch related to the embodiment of the application is prepared by melt blending all components through a double-screw extruder and directly extruding. The temperature of blending is generally 10-50 c above the melting point of the PET copolymer, preferably 20-30 c above the melting point of the PET copolymer, and 50-150 c below the melting point of the anhydride-based chain extender, preferably 120-150 c below the melting point of the chain extender.
The extrusion temperature of the component A chain extender master batch in the preparation process is generally 100-200 ℃, preferably 100-150 ℃; all components are fed from a main feeding port of a double-screw extruder, and are extruded through a porous machine head after the processes of melting plasticization, distribution, dispersion and mixing and the like. The aspect ratio of the twin-screw extruder is 30 to 48, preferably 30 to 36. The screw speed of the extruder is 100 to 200rpm, preferably 150 to 200rpm. The extrudate melt is conveyed into a granulator through air cooling or is granulated by adopting a hot die surface. In the component A chain extender master batch, the concentration of the multifunctional anhydride-based chain extender is 10 to 30wt%, preferably 15 to 20wt%.
The multifunctional epoxide chain extender related to the embodiment of the application adopts one or a combination of two of triglycidyl isocyanurate and styrene-acrylic ester-glycidyl methacrylate copolymer; styrene-acrylate-glycidyl methacrylate copolymers are preferably used.
Embodiments of the present application 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 toughening agent resin is 6-20 g/10min (190 ℃/2.16 kg); preferably 6 to 12g/10min (190 ℃ C./2.16 kg). The content of glycidyl methacrylate GMA in the PET toughening agent resin is 1-10wt%; preferably 2 to 6wt%.
The component B chain extender master batch according to the embodiment of the present application is prepared by melting and mixing the components by a twin screw extruder and directly extruding the components, wherein the blending temperature is 50 to 150 ℃, preferably 60 to 120 ℃. Similarly, all components are fed from a main feeding port of a double-screw extruder, and are extruded through a porous machine head after the processes of melting plasticization, distribution, dispersion mixing and the like. The double-screw extruder is the same as the master batch for preparing the chain extender of the component A, 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. The continuous underwater pelletizing process is adopted to produce the component B chain extender master batch, and the water temperature of the process water for underwater pelletizing is 2-20 ℃, preferably 5-10 ℃. The concentration of epoxide chain extender in the masterbatch of component B chain extender is 20 to 50% by weight, preferably 25 to 35% by weight.
Other kinds of processing aids, such as heat stabilizers, nucleating agents, flame retardants, and the like, may also be added to the chain extender masterbatch according to embodiments of the present application. Common flame retardants for polyesters include halogens, phosphors, inorganic compounds, and the like. Typical foaming nucleating agents are calcium powder, talcum powder, nano clay and SiO 2 Etc.
In the rPET extrusion foaming technique, the intrinsic viscosity of rPET is usually 0.6-0.85 dL/g (test standard GB/T14190, solvent is phenol: tetrachloroethane=1:1w/w, test temperature is 25 ℃ + -0.1 ℃). As the intrinsic viscosity of rPET decreases, the total end group concentration increases. Wherein the concentration of the terminal carboxyl groups is usually 20 to 55mol/T (test standard GB/T14190, which is measured by a solution titration method with 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 properties of the PET raw stock, as well as the heat, mechanical history, etc. during the primary processing and recovery.
In the rPET extrusion foaming process, the rPET raw material can be recycled bottle flakes or rPET particles, and the rPET raw material is used for extrusion foaming after crystallization and drying.
The additive amount of the component A chain extender master batch and the component B chain extender master batch prepared by the method in the rPET extrusion foaming process is 1-6wt%, preferably 1.5-3wt%.
Supercritical fluids such as N can be used in the rPET extrusion foaming process of the present application 2 、CO 2 Alkanes such as butane, pentane, etc., and mixtures of two or more of the foregoing blowing agents as physical blowing agents.
The rPET extrusion foaming process can adopt all types of extrusion foaming units, such as a single-screw extruder, a double-screw extruder, an extrusion unit connected in series (a double-screw extruder is arranged at the upper stage/a single-screw extruder is arranged at the lower stage, and the upper stage and the lower stage are all single-screw extruders), and the extruded foaming rPET products can be sheets, plates, beads, profiled bars and the like by changing the machine head of the foaming extruder and the downstream auxiliary machine of the foaming unit. In addition, the chain extender master batch related to the application can also be used in extrusion foaming processes of other PET raw materials, such as vPET, PET flame-retardant slices, PET copolymers, such as PETG, and mixtures of different PET raw materials, and can also be used for other high-melting polyesters (the melting point is more than or equal to 220 ℃), such as polybutylene terephthalate (PBT) and the like.
The present application is described in further detail below with reference to examples and figures.
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 is as follows: PMDA is selected as a chain extender, and the concentration in the master batch is 20wt%; the Shanghai petrochemical poly (ethylene terephthalate) -co-isophthalate copolymer chips were used as carrier resins with a melting point of 120℃and an intrinsic viscosity of 0.675dL/g and a concentration of 80% by weight in the masterbatch. The length-diameter ratio L/D=48 of the double-screw extruder for master batch preparation, the screw rotating speed is 150rpm, the blending temperature is 120-165 ℃, and the extrudate melt is used for granulating after air cooling to prepare the chain extender master batch.
The preparation method of the component B chain extender master batch 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 2-3wt%, and the melt index is 6g/10min (190 ℃/2.16 kg). The length-diameter ratio L/D=48 of the double-screw extruder for master batch preparation, the screw rotating speed is 200rpm, the blending temperature is 50-100 ℃, the extrudate melt is pelletized under water to prepare the chain extender master batch, and the temperature of the process water for underwater pelletizing is 10 ℃.
Example 2:
a two-component chain extender masterbatch for rPET extrusion foaming differs from example 1 in that the concentration of chain extender in the component A chain extender masterbatch is 10 wt.%, the concentration of carrier resin in the masterbatch is 90 wt.%, and the component B chain extender masterbatch remains identical to example 1.
Example 3:
a two-component chain extender masterbatch for rPET extrusion foaming differs from example 1 in that the concentration of the chain extender in the component A chain extender masterbatch is 30% by weight, the concentration of the carrier resin in the masterbatch is 70% by weight, and the component B chain extender masterbatch remains identical to example 1.
Example 4:
a two-component chain extender masterbatch for rPET extrusion foaming differs from example 1 in that the concentration of the chain extender in the component B chain extender masterbatch is 20% by weight, the concentration of the carrier resin in the masterbatch is 80% by weight, and the component A chain extender masterbatch remains identical to example 1.
Example 5:
a two-component chain extender masterbatch for rPET extrusion foaming differs from example 1 in that the concentration of chain extender in the component B chain extender masterbatch is 50 wt.%, the concentration of carrier resin in the masterbatch is 50 wt.%, and the component A chain extender masterbatch remains identical to example 1.
Example 6:
a two-component chain extender masterbatch for rPET extrusion foaming, which differs from example 1 in that the component B chain extender masterbatch is prepared by the following method: triglycidyl isocyanurate TGIC is selected as a chain extender, the functionality of the triglycidyl isocyanurate TGIC is 3, and the concentration of the triglycidyl isocyanurate TGIC in the master batch is 20wt%; styrene-methyl methacrylate-glycidyl methacrylate copolymer is selected as the carrier resin, the glycidyl methacrylate content 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 master batch preparation, the screw rotating speed is 300rpm, the blending temperature is 50-150 ℃, the extrudate melt is pelletized under water to prepare the chain extender master batch, and the temperature of the process water for underwater pelletizing is 5 ℃. Component a chain extender master batch remained the same as in example 1.
Example 7:
a two-component chain extender masterbatch for rPET extrusion foaming differs from example 1 in that the component A chain extender masterbatch is prepared by the following method: BTDA is selected as a chain extender, and the concentration in the master batch is 25wt%; polyethylene terephthalate-1, 4 cyclohexanedimethanol ester copolymer slices subjected to chemical fiber characterization are used as carrier resins, the melting point is 115 ℃, the intrinsic viscosity is 0.734dL/g, and the concentration in the master batch is 75 weight percent. The length-diameter ratio L/D=44 of the double-screw extruder for master batch preparation, the screw rotating speed is 100rpm, the blending temperature is 100-155 ℃, and the extrudate melt is used for granulating after air cooling to prepare the chain extender master batch; component B chain extender master batch was identical to example 1.
Example 8:
a two-component chain extender masterbatch for rPET extrusion foaming, which differs from example 7 in that the component B chain extender masterbatch is prepared by the following method: triglycidyl isocyanurate TGIC is selected as a chain extender, the functionality of the triglycidyl isocyanurate TGIC is 3, and the concentration of the triglycidyl isocyanurate TGIC in the master batch is 20wt%; styrene-methyl methacrylate-glycidyl methacrylate copolymer is selected as the carrier resin, the glycidyl methacrylate content 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 master batch preparation, the screw rotating speed is 300rpm, the blending temperature is 50-150 ℃, the extrudate melt is pelletized under water to prepare the chain extender master batch, and the temperature of the process water for underwater pelletizing is 5 ℃.
Application example 1:
a preparation method of the foamed rPET board comprises the following steps:
PET extrusion foaming is carried out by adopting a double-screw extruder, wherein the screw diameter D=75mm and the length-diameter ratio L/D=44 of the extruder, and a static mixer and a porous foaming die are sequentially arranged at the downstream of the extruder. The porous mold was 620mm wide and 26mm thick. And (5) enabling the extrudate to enter a leveling machine after exiting the die to obtain the foamed PET board with the rectangular cross section.
The two-component chain extender master batch prepared in example 1 was used for extrusion foaming with rPET intrinsic viscosity IV=0.78 dL/g, terminal carboxyl group concentration 20mol/t and terminal hydroxyl group concentration 60mol/t, wherein rPET was dehydrated and dried at 160℃for 6hr. The PET feed rate was 100kg/hr, the component A chain extender masterbatch feed rate was 1.6kg/hr (1.6 wt%) and the component B chain extender masterbatch feed rate was 2.0kg/hr (2.0 wt%) fed separately by a weight loss feeder. In this example isopentane was used as the blowing agent, which was injected into the extruder by 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 |
| Mould | 260～265 |
Application example 2:
a foamed rPET sheet was different from application example 1 in that the two-component chain extender master batch obtained in example 2 was used, the feed rate of the component A chain extender master batch was 3.3kg/hr (3.3 wt%) and the feed rate of the component B chain extender master batch was 2.0kg/hr (2.0 wt%).
Application example 3:
a foamed rPET sheet was different from application example 1 in that the two-component chain extender master batch obtained in example 3 was used, the feed rate of the component A chain extender master batch was 1.1kg/hr (1.1 wt%) and the feed rate of the component B chain extender master batch was 2.0kg/hr (2.0 wt%).
Application example 4:
a foamed rPET sheet was different from application example 1 in that the two-component chain extender master batch obtained in example 4 was used, the feed rate of the component A chain extender master batch was 1.6kg/hr (1.6 wt%) and the feed rate of the component B chain extender master batch was 3.0kg/hr (3.0 wt%).
Application example 5:
a foamed rPET sheet was different from application example 1 in that the two-component chain extender master batch obtained in example 5 was used, the feed rate of the component A chain extender master batch was 1.6kg/hr (1.6 wt%) and the feed rate of the component B chain extender master batch was 1.2kg/hr (1.2 wt%).
Application example 6:
a foamed rPET sheet was different from application example 1 in that the two-component chain extender master batch obtained in example 6 was used, the feed rate of the component A chain extender master batch was 1.6kg/hr (1.6 wt%) and the feed rate of the component B chain extender master batch was 1.5kg/hr (1.5 wt%).
Application example 7:
a foamed rPET sheet was different from application example 1 in that the two-component chain extender master batch obtained in example 7 was used, the feed rate of the component A chain extender master batch was 1.9kg/hr (1.9 wt%) and the feed rate of the component B chain extender master batch was 2.0kg/hr (2.0 wt%).
Application example 8:
a foamed rPET sheet was different from application example 1 in that the two-component chain extender master batch obtained in example 8 was used, the feed rate of the component A chain extender master batch was 1.9kg/hr (1.9 wt%) and the feed rate of the component B chain extender master batch was 2.2kg/hr (2.2 wt%).
Application example 9:
the foamed rPET sheet was different from application example 1 in that: the intrinsic viscosity of rPET was 0.65dL/g, the carboxyl end group concentration was 40mol/t, the hydroxyl end group concentration was 64mol/t, the feed rate of the component A chain extender masterbatch was 1.7kg/hr (1.7 wt%) and the feed rate of the component B chain extender masterbatch was 4.0kg/hr (4.0 wt%).
Application example 10:
the foamed rPET sheet was different from application example 1 in that: the intrinsic viscosity of rPET was 0.70dL/g, the carboxyl end group concentration was 35mol/t, the hydroxyl end group concentration was 58mol/t, the feed rate of the component A chain extender masterbatch was 1.6kg/hr (1.6 wt%) and the feed rate of the component B chain extender masterbatch was 3.5kg/hr (3.5 wt%).
Application example 11:
the foamed rPET sheet was different from application example 1 in that: the intrinsic viscosity of rPET was 0.85dL/g, the carboxyl end group concentration was 20mol/t, the hydroxyl end group concentration was 50mol/t, the feed rate of the component A chain extender masterbatch was 1.4kg/hr (1.4 wt%) and the feed rate of the component B chain extender masterbatch was 2.0kg/hr (2.0 wt%).
Application example 12:
a preparation method of the foamed rPET board comprises the following steps:
PET extrusion foaming is carried out by adopting a series extruder set, wherein the screw diameter D=95 mm of an upper-stage double-screw extruder and the length-diameter ratio L/D=40 are adopted, and the diameter D=250 mm of a lower-stage single-screw extruder and the length-diameter ratio L/D=30 are adopted. A static mixer and a porous foaming mould are sequentially arranged at the downstream of the extruder. The porous mold was 1200mm wide and 60mm thick. And (5) enabling the extrudate to enter a leveling machine after exiting the die to obtain the foamed PET board with the rectangular cross section.
The two-component chain extender master batch prepared in example 8 was used for extrusion foaming with rPET intrinsic viscosity IV=0.82 dL/g, terminal carboxyl group concentration 20mol/t and terminal hydroxyl group concentration 54mol/t, wherein rPET was dehydrated and dried at 160℃for 6hr. The PET feed rate was 500kg/hr, the component A chain extender masterbatch feed rate was 8.7kg/hr (1.74 wt%) and the component B chain extender masterbatch feed rate was 5kg/hr (1 wt%) with the two being fed separately by a weight loss feeder.
The present embodiment employs supercritical CO 2 As a foaming agent, the foaming agent was injected into the extruder at a rate of 3.5kg/hr by means of an injection pump. The temperature settings for the extrusion process are shown in the following table:
application example 13:
the foamed rPET sheet was different from application example 12 in that: the intrinsic viscosity of rPET was 0.73dL/g, the carboxyl end group concentration was 40mol/t, the hydroxyl end group concentration was 48mol/t, the feed rate of the component A chain extender masterbatch was 7.75kg/hr (1.55 wt%) and the feed rate of the component B chain extender masterbatch was 9.9kg/hr (1.98 wt%).
Application example 14:
a foamed rPET sheet was different from application example 12 in that rPET had an intrinsic viscosity of 0.68dL/g, a terminal carboxyl group concentration of 45mol/t, a terminal hydroxyl group concentration of 52mol/t, a feed rate of the component A chain extender master batch of 8.4kg/hr (1.68 wt%) and a feed rate of the component B chain extender master batch of 11kg/hr (2.2 wt%).
Comparative example 1:
a foaming rPET plate is different from application example 1 in that a bi-component chain extender master batch adopts Shanghai petrochemical polyethylene terephthalate-isophthalic acid glycol copolymer slices as carrier resin, the melting point is 120 ℃, the intrinsic viscosity is 0.675dL/g, two chain extenders adopt PMDA and styrene-acrylic ester-glycidyl methacrylate copolymer (BASF Joncryl ADR-4368), the concentration of PMDA in the master batch is 20%, the concentration of styrene-acrylic ester-glycidyl methacrylate copolymer (BASF Joncryl ADR-4368) in the master batch is 30%, and the concentration of carrier resin in the master batch is 50%; the length-diameter ratio L/D=48 of the double-screw extruder for master batch preparation, the screw rotating speed is 150rpm, the blending temperature is 120-165 ℃, and the extrudate melt is used for granulating after air cooling to prepare the chain extender master batch. The recovered rPET raw material used was the same as in application example 1, and the amount of the two-component chain extender master batch added was 3.6% by weight.
Comparative example 2:
a foaming rPET plate is different from application example 1 in that a bi-component chain extender master batch adopts Shanghai petrochemical polyethylene terephthalate-isophthalic acid glycol copolymer slices as carrier resin, the melting point is 120 ℃, the intrinsic viscosity is 0.675dL/g, two chain extenders adopt 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 carrier resin in the master batch is 50%; the length-diameter ratio L/D=48 of the double-screw extruder for master batch preparation, the screw rotating speed is 150rpm, the blending temperature is 120-165 ℃, and the extrudate melt is used for granulating after air cooling to prepare the chain extender master batch. The recovered rPET raw material used was the same as in application example 1, and the amount of the two-component chain extender master batch added was 3.6% by weight.
Comparative example 3:
the foamed rPET sheet is different from the application example 1 in that the concentration of the chain extender in the two-component chain extender master batch is different, the concentration of the component A chain extender in the component A chain extender master batch is 5wt%, and the concentration of the component B chain extender in the component B chain extender master batch is 10wt%; the recovered rPET raw material was the same as in application example 1, and the amount of the two-component chain extender master batch added was 3.6% by weight.
Comparative example 4:
the foamed rPET sheet is different from the application example 1 in that the concentration of the chain extender in the two-component chain extender master batch is different, the concentration of the component A chain extender in the component A chain extender master batch is 40wt%, and the concentration of the component B chain extender in the component B chain extender master batch is 60wt%; the recovered rPET raw material was the same as in application example 1, and the amount of the two-component chain extender master batch added was 3.6% by weight.
Mechanical property detection is carried out on the foaming rPET plates prepared in the application examples and the comparative examples, and the detection standards and the detection results are shown in the following table:
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as can be seen from the detection results of application examples 1, application examples 6-8, comparative examples 1-2 and the table above, the preparation 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 hydroxyl end and the carboxyl end of rPET, thereby being beneficial to improving the melt strength and the foaming performance of rPET, and further realizing the preparation of the foaming rPET plate with excellent mechanical properties. The two-component chain extender master batches of comparative examples 1 to 2 are obtained by mixing the 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 groups of the recycled rPET raw material have insufficient reaction, which results in insufficient foaming process and reduced mechanical properties of the foamed rPET plate. In addition, compared with comparative examples 1-2, in the component B chain extender master batch, when the PET toughening agent resin is adopted as the carrier resin, the shearing elongation at break of the prepared foaming rPET plate 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 and the bi-component chain extender master batch, which indicates that the molecular weight of the rPET after the chain extension reaction is increased, and the foamed rPET has a wide molecular weight distribution and a long chain branching structure. Referring to FIG. 3, it can be seen that the foamed rPET sheet prepared in application example 1 has good rPET cell morphology, uniform size and high closed cell rate.
As can be seen from the detection results of the combination application examples 1 to 5 and the comparison examples 3 to 4 and the table above, when the concentrations of the two chain extenders in the master batch are different, the prepared foamed rPET plate has excellent mechanical properties by adjusting the addition amounts of the master batch of the two chain extenders in real time; in comparative example 3, when the concentration of the two chain extenders is too low, the foaming process is insufficient when the component A chain extender master batch with the same amount as that of the application example 1 is added, and the mechanical property of the foamed rPET plate is affected; in comparative example 4, when the master batch of the two chain extenders is too high, the addition amount of the master batch in the foaming process is too low, which is not beneficial to the dispersion of the master batch of the chain extender in the rPET matrix, and the mechanical property of the foamed rPET sheet is obviously reduced.
As can be seen from the detection results of application example 1, application examples 9-14 and the table above, when the bi-component chain extender master batch is used for recycling rPET extrusion foaming, when the intrinsic viscosity or end group concentration of the rPET raw material is changed, the concentration of the chain extender in the master batch can be combined, and the use amount 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 foaming product can be maintained, and the foamed rPET plate with excellent comprehensive mechanical properties can be prepared.
Claims (7)
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 adopting a polyfunctional acid anhydride chain extender and a low-melting-point PET copolymer through melt extrusion granulation; wherein the concentration of the multifunctional anhydride chain extender in the component A chain extender master batch is 10-30wt%; 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 multifunctional anhydride chain extender is one or a combination of two of pyromellitic dianhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride;
the component B chain extender master batch is prepared by adopting a multifunctional epoxide chain extender and PET toughening agent resin to carry out melt extrusion granulation; wherein the concentration of the multifunctional epoxide chain extender in the component B chain extender master batch is 20-50wt%; the PET toughening agent resin is one or a combination of two of ethylene-acrylic ester-glycidyl methacrylate copolymer and polyolefin elastomer grafted glycidyl methacrylate.
2. The two-component chain extender masterbatch for rPET extrusion foaming of claim 1, wherein: the low-melting-point PET copolymer is one or any combination of polyethylene terephthalate-isophthalic acid glycol copolymer, polyethylene terephthalate-phthalic acid glycol copolymer, polyethylene terephthalate-1, 4 cyclohexane dimethanol ester copolymer and polyethylene terephthalate-2, 2-dimethyl-1, 3-propylene glycol ester copolymer.
3. The two-component chain extender masterbatch for rPET extrusion foaming of claim 1, wherein: the multifunctional epoxide chain extender is one or a combination of triglycidyl isocyanurate and styrene-acrylic ester-glycidyl methacrylate copolymer.
4. The two-component chain extender masterbatch for rPET extrusion foaming of claim 1, wherein: the melt index of the PET toughening agent resin is 6-20 g/10min.
5. The two-component chain extender masterbatch for rPET extrusion foaming of claim 4, wherein: the content of glycidyl methacrylate GMA in the PET toughening agent resin is 1-10wt%.
6. The preparation method of the bi-component chain extender master batch for rPET extrusion foaming according to any one of claims 1 to 5, which is characterized by comprising the following steps:
the multifunctional anhydride chain extender in the component A chain extender master batch and the low-melting-point PET copolymer are prepared by melt blending, extrusion and granulation; wherein the blending temperature is 10-50 ℃ higher than the melting point of the low-melting-point PET copolymer and is 50-150 ℃ lower than the melting point of the multifunctional anhydride chain extender; the rotating speed of the screw is 100-200 rpm, and the air-cooled granulating or hot die face granulating is carried out;
the multifunctional epoxide chain extender and PET toughening agent resin in the component B chain extender master batch are prepared by melt blending and extrusion granulation, wherein the blending temperature is 50-150 ℃; the rotation speed of the screw is 200-300 rpm, the underwater pelletization process is adopted, and the water temperature of the process water for underwater pelletization is 2-20 ℃.
7. The foamed rPET product prepared by using the bi-component chain extender master batch for rPET extrusion foaming according to any one of claims 1-5, which is characterized in that: the foaming rPET product comprises any one of a foaming rPET sheet, foaming rPET beads and foaming rPET profiled bars, and the addition amount of the bi-component chain extender master batch in the preparation of the foaming rPET product is 1-6wt%.
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| WO2021207951A1 (en) * | 2020-04-15 | 2021-10-21 | 南京越升挤出机械有限公司 | Chain extender masterbatch for pet extrusion foaming, preparation method therefor, and use thereof |
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