The ternary blending system of compatibilizer compatibilizer PET/PE/compatibilizer mainly focuses on the compatibility or interaction between PET and compatibilizer and the compatibility between PE and compatibilizer. These compatibilizers include random copolymers, block copolymers, graft copolymers, ionomers, and the like. According to the mechanism of compatibilization, it can be divided into non-reactive compatibilization, reactive compatibilization, and special interaction compatibilization.
2.1 Non-reactive compatibilizers Compatibilizing PET/PE blends Copolymers with structures similar to PET and PE have a compatibilizing effect on PET/PE blends, such as (styrene/ethylene/butadiene/styrene) ) Copolymer (SEBS), (Styrene/Ethylene/Propylene) Copolymer (S-EP), EPDM, Ethylene Propylene Rubber (EPR), (Polyethylene Terephthalate/Poly) Ethylene) copolymer (PET-b-PE) etc. These copolymers act as "surfactants" at the PET/PE phase interface, reducing the interfacial tension, increasing the interfacial bond strength, and reducing the size of the disperse phase, thereby improving the compatibility of the blend system. Sex.
Traugott et al. used SEBS and EPR as compatibilizers for PET/HDPE blends and studied the effect of compatibilizer content on the morphology and properties of the blends. With the increase of SEBS content, the strength and rigidity of PET/HDPE decreased; if only a small amount of SEBS was added, the elongation at break could be significantly improved. After the SEBS content reached 20%, the range of the Instron universal material testing machine was reached. The blend was not broken. EPR is much worse than SEBS.
Curry et al. studied the effect of S-EP as a compatibilizer on the mechanical properties of recycled polyethylene terephthalate/recycled high-density polyethylene (RPET/RHDPE) blends, which was considered to be due to the styrene chain of S-EP. The segment is compatible with PET with similar solubility parameters, and S-EP is compatible with PE and can reduce the crystallinity of PE. Therefore, S-EP has good compatibilization for PET/HDPE in a large content range. effect. Even with the formation of a crystalline continuous phase, the blend still has good toughness and impact properties.
2.2 Reactive Compatibilizer Compatibilization PET/PE Co-Mixture Gold Reactive Compatibilizer Compatibilization PET/PE blend system is an effective means to improve PET/PE compatibility. Such compatibilizers mainly include polyolefins. Branches and block copolymers. From the structural point of view, their matrix is ​​compatible with PE, and the functional groups such as epoxy groups, acid anhydride groups, carboxyl groups, and ester groups are added to and esterified with hydroxyl, carboxyl, and ester groups in PET. Reactions such as ester interchange and "in situ" formation of copolymers act as compatibilizers. Among them, graft copolymers and block copolymers of glycidyl methacrylate and olefins are the most effective.
(1) Maleic anhydride (MAH) graft copolymer compatibilizer MAH graft compatibilizer includes polyethylene grafted maleic anhydride (PE-g-MAH), (styrene/ethylene/butadiene/benzene Ethylene) copolymer grafted with maleic anhydride (SEBS-g-MAH), (ethylene/methyl acrylate/maleic anhydride) copolymer (E-MeA-g-MAH) and the like. Because maleic anhydride can only partially reversibly esterify with the hydroxyl end groups of PET at high temperatures, the chemical reactivity between PET and MAH grafts is poor under the blending conditions. Therefore, the interfacial interactions are mainly dispersive forces. And acid-base effect. In order to further improve the interface interaction, an epoxy compound interface modifier may be added. Among the MAH grafts, SEBS-g-MAH has the best compatibilizing effect. The blends with 2% SEBS-g-MAH compatibilized PET/PE (50/50) blends were broken. 600% elongation "super-tough" blend.
(2) glycidyl methacrylate (GMA) graft or copolymer compatibilizer GMA graft or copolymer compatibilizer including polyethylene grafted glycidyl methacrylate (PE-g-GMA), (ethylene / Glycidyl methacrylate) copolymer (E-GMA), (ethylene/ethyl acrylate/glycidyl methacrylate) copolymer (E-EA-GMA), and the like. GMA can react with both the hydroxyl end of PET and the carboxyl end of PET, and the copolymer formed in situ at the interface of the blend has good compatibilization. By comparing the morphological structure, rheological properties, thermal properties and mechanical properties of the blends, the commonly used MAH and GMA modified copolymer compatibilization has the following order: E-GMA>E-EA-GMA>SEBS-g -MAH>E-MeA-g-MAH, it can be seen that GMA modified copolymers are good PET/PE compatibilizers.
(3) Other functional copolymer compatibilizers Functional copolymers with carboxyl, ester, and amide structures also have a compatibilizing effect on PET/PE blends, such as polyethylene grafted methyl methacrylate (PE) -g-MMA), polyethylene grafted hydroxyethyl methacrylate (PE-g-HEMA), polyethylene grafted ethyl acrylate (PE-g-EA), polyethylene grafted maleimide (PE) -g-MI), (Ethylene/Vinyl Acetate) Copolymers (E/VAC), (Ethylene/Acrylic Acid) Copolymers (EAA), etc. Most of these copolymers are PET/PE copolymerized by esterification or transesterification. Mixed system of capacity expansion. Since the esterification or transesterification reaction cannot be sufficiently performed at the processing temperature, it is difficult to obtain a good compatibilization effect.
In order to promote esterification or transesterification, He Hui et al. studied the compatibilization of HDPE/PET (75/25) blends with E/VAC and EAA catalyzed by transition metal catalysts. Chemical analysis and spectroscopic analysis show that the copolymer formed "in situ" by catalyzed esterification or transesterification acts as a compatibilizer; under the action of the catalyst, E/VAC, EAA improves the flow of HDPE/PET blended gold The performance was improved, and the heat resistance of HDPE was improved. The tensile and impact properties of the ternary blend were significantly higher than those of the HDPE/PET blend. It has guiding significance for high-performance HDPE.
2.3 New Methods, Special Compatibilizers Compatibilization of PET/HDPE Alloys With the diversification of blend modification and processing methods, new means of electron irradiation have also been applied to the blend modification of PET/PE. The ionomer compatibilizer is a special compatibilizer that has attracted research interest in recent years. For a blend system containing a crystalline polymer, the ionomer can play both a compatibilizing function and a crystallization nucleating agent. The interaction between the ionomer compatibilizer and the PET may have special effects such as ion-dipole, complex coordination, and physical cross-linking of ion clusters in addition to possible esterification and transesterification reactions.
Kalfoglou used an (ethylene/acrylic acid) copolymer sodium salt (Surlyn 1605) as a compatibilizer for PET/LLDPE blends to study the compatibilization of different PET/LLDPE ratios and Surlyn content. The blend PET/LLDPE/surlyn (68.2/22.7/9.1) has good mechanical properties. Based on the study of the compatibility of PET/Surlyn blends, it is believed that the strong interaction between the PET/Surlyn two-phase interface is the root cause of compatibilization.
MascaJ et al. mixed the phenoxy polymer (polyhydroxy ether of bisphenol A) with maleic anhydride of an ethylene-propylene copolymer to obtain a graft copolymer, which was mixed with a sodium salt of (ethylene/acrylic acid) copolymer (Surlyn 8660). Sodium phenoxide and sodium ethoxide enhance the ionic character to give isoionic mixtures, and the grafts and blends are used for compatibilization. Both of these compatibilizers facilitate the dispersion of PET or HDPE because they are all effective surfactants. The addition of ionomers continuously increases the melt viscosity of the blend, but only the isoionic mixture produces a substantial improvement in the tensile strength and elongation at break of the blend, since the blend has very high crystallization of the blend. Strong nucleation and enhanced polymer two-phase interface bonding.
Xi Shiping et al. studied the effect of low density polyethylene grafted maleic anhydride (LDPE-g-MALa) on the crystallization behavior and mechanical properties of PET/LDPE blends. The blend impact strength of PET/LDPE/LDPE-g-MALa(80/18/2) system is 40% higher than that of PET, and the tensile strength is increased by 25%; it is higher than that of PET/LDPE (80/20). 170% and 30%. When the content of ionomer increases to 5%, the overall performance decreases. The increase of ionomer content, the increase of melt crystallization temperature (Tcc), the decrease of cold crystallization temperature (Tch), the increase of Tcc indicate that the ionomer has a nucleation effect on PET, and the decrease of Tch indicates that the ionomer has a supple molecular chain to PET. Molecular motion has a definite promoting effect.
3 Application prospects of PET/PE blended gold The purpose of PE modified PET is to improve the rheological properties of PET, to accelerate the crystallization speed of PET, to increase the impact properties of PET, and to reduce the water absorption of PET so as to obtain high tensile strength. Tensile strength, high toughness, high crystallinity, high temperature resistant blended gold. This has a wide application prospect for the use of low-cost PET to replace other high-priced engineering plastics for electronic appliances, transportation, and mechanical instrumentation, and to make full use of large amounts of recycled PET.
The purpose of modifying the PE with PET is to improve the mechanical properties and heat resistance of the PE, thereby obtaining a high-performance PE. If appropriate processing methods are adopted to disperse PET in a layered structure in a PE matrix, the solvent resistance of PET can be used to improve the barrier properties of packaging products and hollow containers made of PE alloys. Jin Sun, et al. EDA compatibilized HDPE/PET (80/20) blend system and obtained a layered dispersion structure with PET as the dispersed phase. The lamellar tendency of PET increases with the phase compatibility of the system, but when the content of the compatibilizer exceeds a certain value, the lamellar dispersed phase begins to be destroyed from the center. The low melting temperature, low shear rate and high forming temperature are favorable for the maintenance of the large size of the disperse phase, the occurrence of radial deformation, and the formation of lamellar dispersion structures.
4 Conclusion In the PET/PE blended gold system, no matter which type of alloy blend modification, to improve the overall performance of PET and PE, broaden the scope of application of PET and PE, especially the recycling of PET or PE have practical significance.
2.1 Non-reactive compatibilizers Compatibilizing PET/PE blends Copolymers with structures similar to PET and PE have a compatibilizing effect on PET/PE blends, such as (styrene/ethylene/butadiene/styrene) ) Copolymer (SEBS), (Styrene/Ethylene/Propylene) Copolymer (S-EP), EPDM, Ethylene Propylene Rubber (EPR), (Polyethylene Terephthalate/Poly) Ethylene) copolymer (PET-b-PE) etc. These copolymers act as "surfactants" at the PET/PE phase interface, reducing the interfacial tension, increasing the interfacial bond strength, and reducing the size of the disperse phase, thereby improving the compatibility of the blend system. Sex.
Traugott et al. used SEBS and EPR as compatibilizers for PET/HDPE blends and studied the effect of compatibilizer content on the morphology and properties of the blends. With the increase of SEBS content, the strength and rigidity of PET/HDPE decreased; if only a small amount of SEBS was added, the elongation at break could be significantly improved. After the SEBS content reached 20%, the range of the Instron universal material testing machine was reached. The blend was not broken. EPR is much worse than SEBS.
Curry et al. studied the effect of S-EP as a compatibilizer on the mechanical properties of recycled polyethylene terephthalate/recycled high-density polyethylene (RPET/RHDPE) blends, which was considered to be due to the styrene chain of S-EP. The segment is compatible with PET with similar solubility parameters, and S-EP is compatible with PE and can reduce the crystallinity of PE. Therefore, S-EP has good compatibilization for PET/HDPE in a large content range. effect. Even with the formation of a crystalline continuous phase, the blend still has good toughness and impact properties.
2.2 Reactive Compatibilizer Compatibilization PET/PE Co-Mixture Gold Reactive Compatibilizer Compatibilization PET/PE blend system is an effective means to improve PET/PE compatibility. Such compatibilizers mainly include polyolefins. Branches and block copolymers. From the structural point of view, their matrix is ​​compatible with PE, and the functional groups such as epoxy groups, acid anhydride groups, carboxyl groups, and ester groups are added to and esterified with hydroxyl, carboxyl, and ester groups in PET. Reactions such as ester interchange and "in situ" formation of copolymers act as compatibilizers. Among them, graft copolymers and block copolymers of glycidyl methacrylate and olefins are the most effective.
(1) Maleic anhydride (MAH) graft copolymer compatibilizer MAH graft compatibilizer includes polyethylene grafted maleic anhydride (PE-g-MAH), (styrene/ethylene/butadiene/benzene Ethylene) copolymer grafted with maleic anhydride (SEBS-g-MAH), (ethylene/methyl acrylate/maleic anhydride) copolymer (E-MeA-g-MAH) and the like. Because maleic anhydride can only partially reversibly esterify with the hydroxyl end groups of PET at high temperatures, the chemical reactivity between PET and MAH grafts is poor under the blending conditions. Therefore, the interfacial interactions are mainly dispersive forces. And acid-base effect. In order to further improve the interface interaction, an epoxy compound interface modifier may be added. Among the MAH grafts, SEBS-g-MAH has the best compatibilizing effect. The blends with 2% SEBS-g-MAH compatibilized PET/PE (50/50) blends were broken. 600% elongation "super-tough" blend.
(2) glycidyl methacrylate (GMA) graft or copolymer compatibilizer GMA graft or copolymer compatibilizer including polyethylene grafted glycidyl methacrylate (PE-g-GMA), (ethylene / Glycidyl methacrylate) copolymer (E-GMA), (ethylene/ethyl acrylate/glycidyl methacrylate) copolymer (E-EA-GMA), and the like. GMA can react with both the hydroxyl end of PET and the carboxyl end of PET, and the copolymer formed in situ at the interface of the blend has good compatibilization. By comparing the morphological structure, rheological properties, thermal properties and mechanical properties of the blends, the commonly used MAH and GMA modified copolymer compatibilization has the following order: E-GMA>E-EA-GMA>SEBS-g -MAH>E-MeA-g-MAH, it can be seen that GMA modified copolymers are good PET/PE compatibilizers.
(3) Other functional copolymer compatibilizers Functional copolymers with carboxyl, ester, and amide structures also have a compatibilizing effect on PET/PE blends, such as polyethylene grafted methyl methacrylate (PE) -g-MMA), polyethylene grafted hydroxyethyl methacrylate (PE-g-HEMA), polyethylene grafted ethyl acrylate (PE-g-EA), polyethylene grafted maleimide (PE) -g-MI), (Ethylene/Vinyl Acetate) Copolymers (E/VAC), (Ethylene/Acrylic Acid) Copolymers (EAA), etc. Most of these copolymers are PET/PE copolymerized by esterification or transesterification. Mixed system of capacity expansion. Since the esterification or transesterification reaction cannot be sufficiently performed at the processing temperature, it is difficult to obtain a good compatibilization effect.
In order to promote esterification or transesterification, He Hui et al. studied the compatibilization of HDPE/PET (75/25) blends with E/VAC and EAA catalyzed by transition metal catalysts. Chemical analysis and spectroscopic analysis show that the copolymer formed "in situ" by catalyzed esterification or transesterification acts as a compatibilizer; under the action of the catalyst, E/VAC, EAA improves the flow of HDPE/PET blended gold The performance was improved, and the heat resistance of HDPE was improved. The tensile and impact properties of the ternary blend were significantly higher than those of the HDPE/PET blend. It has guiding significance for high-performance HDPE.
2.3 New Methods, Special Compatibilizers Compatibilization of PET/HDPE Alloys With the diversification of blend modification and processing methods, new means of electron irradiation have also been applied to the blend modification of PET/PE. The ionomer compatibilizer is a special compatibilizer that has attracted research interest in recent years. For a blend system containing a crystalline polymer, the ionomer can play both a compatibilizing function and a crystallization nucleating agent. The interaction between the ionomer compatibilizer and the PET may have special effects such as ion-dipole, complex coordination, and physical cross-linking of ion clusters in addition to possible esterification and transesterification reactions.
Kalfoglou used an (ethylene/acrylic acid) copolymer sodium salt (Surlyn 1605) as a compatibilizer for PET/LLDPE blends to study the compatibilization of different PET/LLDPE ratios and Surlyn content. The blend PET/LLDPE/surlyn (68.2/22.7/9.1) has good mechanical properties. Based on the study of the compatibility of PET/Surlyn blends, it is believed that the strong interaction between the PET/Surlyn two-phase interface is the root cause of compatibilization.
MascaJ et al. mixed the phenoxy polymer (polyhydroxy ether of bisphenol A) with maleic anhydride of an ethylene-propylene copolymer to obtain a graft copolymer, which was mixed with a sodium salt of (ethylene/acrylic acid) copolymer (Surlyn 8660). Sodium phenoxide and sodium ethoxide enhance the ionic character to give isoionic mixtures, and the grafts and blends are used for compatibilization. Both of these compatibilizers facilitate the dispersion of PET or HDPE because they are all effective surfactants. The addition of ionomers continuously increases the melt viscosity of the blend, but only the isoionic mixture produces a substantial improvement in the tensile strength and elongation at break of the blend, since the blend has very high crystallization of the blend. Strong nucleation and enhanced polymer two-phase interface bonding.
Xi Shiping et al. studied the effect of low density polyethylene grafted maleic anhydride (LDPE-g-MALa) on the crystallization behavior and mechanical properties of PET/LDPE blends. The blend impact strength of PET/LDPE/LDPE-g-MALa(80/18/2) system is 40% higher than that of PET, and the tensile strength is increased by 25%; it is higher than that of PET/LDPE (80/20). 170% and 30%. When the content of ionomer increases to 5%, the overall performance decreases. The increase of ionomer content, the increase of melt crystallization temperature (Tcc), the decrease of cold crystallization temperature (Tch), the increase of Tcc indicate that the ionomer has a nucleation effect on PET, and the decrease of Tch indicates that the ionomer has a supple molecular chain to PET. Molecular motion has a definite promoting effect.
3 Application prospects of PET/PE blended gold The purpose of PE modified PET is to improve the rheological properties of PET, to accelerate the crystallization speed of PET, to increase the impact properties of PET, and to reduce the water absorption of PET so as to obtain high tensile strength. Tensile strength, high toughness, high crystallinity, high temperature resistant blended gold. This has a wide application prospect for the use of low-cost PET to replace other high-priced engineering plastics for electronic appliances, transportation, and mechanical instrumentation, and to make full use of large amounts of recycled PET.
The purpose of modifying the PE with PET is to improve the mechanical properties and heat resistance of the PE, thereby obtaining a high-performance PE. If appropriate processing methods are adopted to disperse PET in a layered structure in a PE matrix, the solvent resistance of PET can be used to improve the barrier properties of packaging products and hollow containers made of PE alloys. Jin Sun, et al. EDA compatibilized HDPE/PET (80/20) blend system and obtained a layered dispersion structure with PET as the dispersed phase. The lamellar tendency of PET increases with the phase compatibility of the system, but when the content of the compatibilizer exceeds a certain value, the lamellar dispersed phase begins to be destroyed from the center. The low melting temperature, low shear rate and high forming temperature are favorable for the maintenance of the large size of the disperse phase, the occurrence of radial deformation, and the formation of lamellar dispersion structures.
4 Conclusion In the PET/PE blended gold system, no matter which type of alloy blend modification, to improve the overall performance of PET and PE, broaden the scope of application of PET and PE, especially the recycling of PET or PE have practical significance.
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