CN112961472B - Modified polyethylene glycol furan dicarboxylate and preparation method and application thereof - Google Patents
Modified polyethylene glycol furan dicarboxylate and preparation method and application thereof Download PDFInfo
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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Abstract
The invention relates to a modified polyethylene glycol furan dicarboxylate, which comprises the following components in parts by weight: 88-96.6 parts of polyethylene furan dicarboxylate, 3-10 parts of polybutylene succinate, 0.3-1 part of chain extender and 0.1-1 part of antioxidant. The modified polyethylene glycol furan dicarboxylate disclosed by the invention has the characteristics of high strength, high rigidity, good toughness and the like, and simultaneously keeps excellent gas barrier property. The preparation method of the modified polyethylene glycol furan dicarboxylate is simple, and can be applied to the field of plastic packaging materials with high requirements on gas barrier property.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to modified polyethylene glycol furanoate, and also relates to a preparation method and application of the high polymer material.
Background
Polyethylene furandicarboxylate (PEF) is a polymer material which is more and more emphasized at present, compared with petroleum-based polyethylene terephthalate (PET), the bio-based polyethylene furandicarboxylate (PEF) has more excellent mechanical property, heat resistance and gas barrier property, and has a very wide application prospect in the field of high-barrier packaging materials. However, the asymmetry of the furan ring itself and the oxygen atom on the furan ring give the PEF a large polarity, which results in that the PEF molecular chain is not easy to move, so that the PEF shows obvious brittleness, the breaking elongation of which is less than 5%, and the impact strength is only 3KJ/m 2 And the application of the PEF in the field of plastic packaging materials is greatly limited. Thus, it is necessary to modify the toughness of PEF to improve its ductility and impact resistance, while maintaining high strength and stiffness, as well as good gas barrier properties.
At present, there are two main methods for toughening and modifying PEF. The first toughening method is to introduce binary acid or diol monomer containing flexible chain segment or symmetrical rigid structure for copolymerization modification. However, copolymerization with a dibasic acid reduces the furan ring content, resulting in a significant decrease in the gas barrier properties of the material. In the copolymerization with a diol having a soft segment, it is often difficult to achieve both strength and toughness. For example, in the case of copolyesters (PEFEGs) obtained by copolymerizing 2, 5-furandicarboxylic acid, ethylene glycol and polyethylene glycol (Polymer Degradation and Stability,2017,144:121-127), when the amount of polyethylene glycol having a molecular weight of 6000 added reaches 80 wt%, the elongation at break reaches 61%, but the tensile strength is only 12MPa, which is 83% lower than that of PEF; copolymerization with a diol having a symmetrical rigid ring structure can improve the elongation at break of the PEF while maintaining high gas barrier properties, strength and rigidity, but such comonomers are expensive and have very limited improvement in impact toughness of the PEF. For example, the introduction of 75 mol% of 1, 4-cyclohexanediol monomer copolymerized with 2, 5-furandicarboxylic acid and ethylene glycol (Green Chemistry,2016,18: 5142-. In addition, the copolymerization modification method is very complicated in process and poor in operability.
Another method for toughening the PEF is to perform melt blending modification on the PEF and a flexible polymer, and the method can realize the advantage complementation of the performances of all components and obtain a material with ideal comprehensive performance. PEF is toughened by poly (butylene terephthalate)/adipate terephthalate (PBAT) by a Zhongguang team of the institute of applied chemistry for Changchun (New Journal of chemistry,2020,44: 3112-one 3121), and when the content of the PBAT is 50%, the elongation at break and the impact strength of a sample of the PBAT/PEF 50% are remarkably improved, but the strength and the rigidity of the sample are greatly reduced at the same time. Yangyuan et al (Chinese Journal of Polymer Science,2020,38:1099-1106) toughened PEF with polyamide 11(PA11), when PA11 content is 20% and 1.5 parts of reactive compatilizer is added, elongation at break of the material is increased from 3.6% to 90.1%, and impact strength is increased from 3.8KJ/m 2 Increased to 16.7KJ/m 2 And meanwhile, the strength and the rigidity of the composite material are not obviously reduced. Unfortunately, some degradation of PA11 occurred at this melt processing temperature (230 ℃), and the gas barrier properties of PEF materials were significantly reduced with the addition of 20 wt% PA 11.
In summary, for the application of PEF in the field of plastic packaging, the disadvantage of high brittleness needs to be solved. In the aspect of toughening of PEF, a number of disadvantages still exist at present, which are specifically indicated that it is difficult to simultaneously improve toughness and maintain strength, rigidity and barrier property of PEF. Therefore, it is an urgent problem to prepare a PEF material with good stiffness, flexibility and barrier property by a proper toughening method.
Disclosure of Invention
Aiming at the defects in the prior art, the invention selects a proper auxiliary agent to improve the polyethylene glycol furandicarboxylate, and the modified polyethylene glycol furandicarboxylate has the characteristics of high strength, high rigidity, good toughness, excellent barrier property and the like, can be applied to plastic packaging materials, and has low cost and huge market application prospect.
In order to solve the above technical problems, the present invention is solved by the following technical solutions.
The modified polyethylene glycol furan dicarboxylate comprises the following components in parts by weight: 88-96.6 parts of polyethylene glycol furan dicarboxylate; 3-10 parts of poly (butylene succinate); 0.3-1 part of a chain extender; 0.1-1 part of antioxidant.
In order to improve the toughness of the PEF, polybutylene succinate (PBS) with excellent thermal stability is used as a toughening component, and the strength and rigidity of the PEF are inevitably reduced greatly by adding a large amount of PBS into the PEF due to the fact that the tensile strength and the elastic modulus of the PBS are not high, so that the PBS is added in an amount of 3-10 parts through continuous experimental trial and optimization.
In a preferred embodiment, the modified polyethylene furandicarboxylate comprises the following components in parts by weight: 88.4-93.4 parts of polyethylene glycol furan dicarboxylate; 5-10 parts of poly (butylene succinate); 0.5-1 part of a chain extender; 0.6 part of antioxidant.
In a preferred embodiment, the modified polyethylene furandicarboxylate comprises the following components in parts by weight: 93.4 parts of polyethylene furan dicarboxylate; 5 parts of polybutylene succinate; 1 part of a chain extender; 0.6 part of antioxidant.
In a preferred embodiment, the intrinsic viscosity of the polyethylene furandicarboxylate is 0.65-0.85 dL/g, and the performance of the prepared product is optimal.
In a preferred embodiment, the chain extender is a styrene-acrylate-glycidyl acrylate copolymer. Due to poor compatibility between PEF and PBS, effective toughening of PEF is difficult with the addition of only flexible PBS. In the invention, the main function of adding the chain extender containing the polyepoxy functional group into the PEF/PBS blending system is to improve the compatibility of PEF and PBS. A plurality of epoxy functional groups in the chain extender can react with terminal hydroxyl and terminal carboxyl on molecular chains of PEF and PBS simultaneously to generate a graft copolymer PEF-g-PBS (the reaction mechanism is shown in figure 1), the graft copolymer not only can effectively reduce the surface tension of the PBS to enable the PBS to be dispersed in PEF matrix resin in a smaller size, but also can improve the compatibility of the PEF and the PBS, improve the interface bonding force of the PEF and the PBS and finally improve the mechanical property of the PEF/PBS blend.
When the addition amount of the chain extender is low, the formed graft copolymer is less, and the toughening effect is limited; and when the addition amount of the chain extender is higher, the melt viscosity of the blending system is obviously increased, and the secondary processing molding of the material is not facilitated. Therefore, the addition amount of the chain extender in the present invention is 0.3 to 1 part. Preferably, the addition amount of the chain extender is 0.5-1 part.
In a preferred embodiment, the antioxidant is compounded by hindered phenol antioxidant and phosphite antioxidant according to the weight ratio of 1: 1.
The preparation method of the modified polyethylene glycol furandicarboxylate comprises the following steps: s10: drying polyethylene furandicarboxylate and polybutylene succinate in a vacuum oven at 80 ℃ for 4 h; s20: adding the dried polyethylene glycol furandicarboxylate and polybutylene succinate, a chain extender and an antioxidant into a double-screw extruder according to a ratio, and extruding and granulating after melt blending to obtain the modified polyethylene glycol furandicarboxylate granules.
In a preferred embodiment, in step S20, the screw rotation speed of the twin-screw extruder is 80 to 120 rpm; the melt blending temperature is 225-235 ℃, and the melt blending time is 4-8 min.
In a preferred embodiment, the weight ratio of the components in step S20 is as follows: 88-96.6 parts of polyethylene glycol furan dicarboxylate; 3-10 parts of poly (butylene succinate); 0.3-1 part of a chain extender; 0.1-1 part of antioxidant.
The application of the modified polyethylene furan dicarboxylate in the plastic product is preferably the application in the field of plastic packaging materials, and the modified polyethylene furan dicarboxylate is the modified polyethylene furan dicarboxylate.
Compared with the prior art, the invention has the following beneficial effects: (1) the modified polyethylene glycol furan dicarboxylate is prepared by taking PEF, PBS and a chain extender as raw materials and performing melt blending, and the preparation method is simple, convenient and feasible, has low cost, is beneficial to large-scale production and application, and has huge market prospect.
(2) The modified polyethylene glycol furandicarboxylate prepared by the invention is a rigid-flexible material, namely the material has the characteristics of high strength, high rigidity, good toughness and the like. The modified polyethylene furan dicarboxylate has excellent barrier property due to the fact that the addition amount of PBS in the modified polyethylene furan dicarboxylate is low.
Drawings
FIG. 1 is a reaction a which may occur in the production of a graft copolymer: the carboxyl end groups of the PEF react with the chain extender.
FIG. 2 is a reaction b which may occur in the production of graft copolymers: the terminal carboxyl groups of PBS were reacted with chain extenders.
FIG. 3 is a stress-strain curve of the samples of examples 1 to 4 in the present application.
FIG. 4 is a stress-strain curve of the samples of comparative examples 1 to 4 in the present application.
Above, in fig. 1 and 2: r 1 ～R 5 Is H, CH 3 Or other alkyl groups; r 6 Is an alkyl group; x, y and z are values between 1 and 20.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example 1
And drying the polyethylene furan dicarboxylate and the polybutylene succinate in a vacuum oven at 80 ℃ for 4 hours. 93.9 parts of polyethylene furandicarboxylate, 5 parts of polybutylene succinate, 0.5 part of styrene-acrylate-glycidyl acrylate copolymer and 0.6 part of antioxidant (antioxidant 1010 and antioxidant 168 are compounded according to a ratio of 1: 1) are weighed, uniformly mixed, added into a double-screw extruder together, melted and blended for 5min, extruded and granulated, the melting and blending temperature is 230 ℃, and the screw rotating speed is 100 rpm.
Example 2
And drying the polyethylene furan dicarboxylate and the polybutylene succinate in a vacuum oven at 80 ℃ for 4 hours. 93.4 parts of polyethylene furandicarboxylate, 5 parts of polybutylene succinate, 1 part of styrene-acrylate-glycidyl acrylate copolymer and 0.6 part of antioxidant (antioxidant 1010 and antioxidant 168 are compounded in a ratio of 1: 1) are weighed, uniformly mixed, added into a rod extruder together, melted and blended for 6min, and then extruded and granulated, wherein the melting and blending temperature is 230 ℃, and the rotating speed of a screw is 100 rpm.
Example 3
And drying the polyethylene furan dicarboxylate and the polybutylene succinate in a vacuum oven at 80 ℃ for 4 hours. Weighing 88.9 parts of polyethylene furandicarboxylate, 10 parts of polybutylene succinate, 0.5 part of styrene-acrylate-glycidyl acrylate copolymer and 0.6 part of antioxidant (antioxidant 1010 and antioxidant 168 are compounded according to a ratio of 1: 1), uniformly mixing, adding into a double-screw extruder, melting and blending for 5min, extruding and granulating, wherein the melting and blending temperature is 235 ℃, and the screw rotating speed is 110 rpm.
Example 4
The polyethylene furandicarboxylate and the polybutylene succinate are dried for 4 hours in a vacuum oven at 80 ℃. Weighing 88.4 parts of polyethylene furandicarboxylate, 10 parts of polybutylene succinate, 1 part of styrene-acrylate-glycidyl acrylate copolymer and 0.6 part of antioxidant (antioxidant 1010 and antioxidant 168 are compounded in a ratio of 1: 1), uniformly mixing, adding into a double-screw extruder, melting and blending for 6min, and then extruding and granulating, wherein the melting and blending temperature is 235 ℃, and the screw rotating speed is 110 rpm.
Comparative example 1
Drying polyethylene glycol furandicarboxylate in a vacuum oven at 80 ℃ for 4h, adding 99.4 parts of polyethylene glycol furandicarboxylate and 0.6 part of antioxidant (antioxidant 1010 and antioxidant 168 are compounded according to a ratio of 1: 1) into a double-screw extruder, melting and processing for 5min, and then extruding and granulating, wherein the melting and processing temperature is 235 ℃, and the screw rotation speed is 80 rpm.
Comparative example 2
And drying the polyethylene furan dicarboxylate and the polybutylene succinate in a vacuum oven at 80 ℃ for 4 hours. Weighing 94.4 parts of polyethylene furandicarboxylate, 5 parts of polybutylene succinate and 0.6 part of antioxidant (antioxidant 1010 and antioxidant 168 are compounded in a ratio of 1: 1), uniformly mixing, adding into a double-screw extruder, melting and blending for 5min, and then extruding and granulating, wherein the melting and blending temperature is 230 ℃, and the screw rotating speed is 100 rpm.
Comparative example 3
And drying the polyethylene furan dicarboxylate and the polybutylene succinate in a vacuum oven at 80 ℃ for 4 hours. 89.4 parts of polyethylene furandicarboxylate, 10 parts of polybutylene succinate and 0.6 part of antioxidant (antioxidant 1010 and antioxidant 168 are compounded in a ratio of 1: 1) are weighed, uniformly mixed, added into a double-screw extruder together, melted and blended for 5min, and then extruded and granulated, wherein the melting and blending temperature is 235 ℃, and the rotating speed of a screw is 110 rpm.
Comparative example 4
And drying the polyethylene furan dicarboxylate and the polybutylene succinate in a vacuum oven at 80 ℃ for 4 hours. Weighing 78.4 parts of polyethylene furandicarboxylate, 20 parts of polybutylene succinate, 1 part of styrene-acrylate-glycidyl acrylate copolymer and 0.6 part of antioxidant (antioxidant 1010 and antioxidant 168 are compounded in a ratio of 1: 1), uniformly mixing, adding into a double-screw extruder, melting and blending for 6min, and then extruding and granulating, wherein the melting and blending temperature is 230 ℃, and the screw rotating speed is 120 rpm.
After the pellets of examples 1-4 and comparative examples 1-4 were prepared into sample bars, tensile property test (GB/T1040.1-2006), Izod impact property test (GB/T1843-. The stress-strain curves of the samples are shown in FIG. 1, and the test results are shown in Table 1.
Table 1 shows the mechanical properties and gas barrier properties of the samples of examples 1 to 4 and comparative examples 1 to 4
a 1 barrer＝10 -10 cm 3 ·cm/cm 2 ·s·cmHg
As can be seen from comparative example 1, pure PEF has high tensile strength, modulus of elasticity and excellent gas barrier properties, but is more brittle, and has 3.9% elongation at break and 3.6KJ/m of impact strength, respectively 2 . When 5% PBS was added (comparative example 2), the toughness was improved to some extent and the elongation at break and impact strength reached 11.2% and 5.7KJ/m, respectively 2 However, when the content of PBS was increased to 10% (comparative example 3), the toughness of the modified PEF was rather deteriorated. The surface tension of PBS in the system is larger, the PBS content is increased and then the PBS content is dispersed in PEF matrix in larger size, and the compatibility between PEF and PBS is not good, so that the toughness of PEF is deteriorated.
After a chain extender containing multi-epoxy functional groups is added into a PEF and PBS system (examples 1-4), each epoxy group in the chain extender can simultaneously react with terminal carboxyl and terminal hydroxyl on molecular chains of the PEF and the PBS to form a PEF-g-PBS graft copolymer, and the graft copolymer plays a role of a 'bridge' of a compatilizer in the system, so that the compatibility between two phases of the PEF and the PBS is improved, the bonding force of a two-phase interface is improved, and the toughness of the material is improved. As can be seen from example 2, when the content of PBS is 5% and the addition amount of the chain extender containing polyepoxy functional group is 1%, the toughness of the modified PEF is significantly improved, and the elongation at break and the impact strength thereof respectively reach 114.3% and 12.0KJ/m 2 Meanwhile, the tensile strength and the elastic modulus of the material are not greatly reduced.
It is worth mentioning that the O of PEF is modified as the PBS content increases 2 Barrier and CO 2 The barrier properties gradually decrease. Therefore, when the PBS content is small (5 wt%), by adding the reactive compatibilizer, a composition having high strength can be obtainedThe modified PEF material has the characteristics of high rigidity, good toughness, excellent barrier property and the like, and can be applied to plastic packaging materials with high requirements on gas barrier property.
The scope of the present invention includes, but is not limited to, the above embodiments, and the present invention is defined by the appended claims, and any alterations, modifications, and improvements that can be easily made by those skilled in the art are all within the scope of the present invention.
Claims (4)
1. The modified polyethylene glycol furan dicarboxylate is characterized by comprising the following components in parts by weight: 93.4 parts of polyethylene furan dicarboxylate; 5 parts of polybutylene succinate; 1 part of a chain extender; 0.6 part of antioxidant;
the intrinsic viscosity of the polyethylene glycol furandicarboxylate is 0.65-0.85 dL/g;
the chain extender is a styrene-acrylate-glycidyl acrylate copolymer;
the antioxidant is prepared by compounding hindered phenol antioxidant and phosphite antioxidant according to the weight ratio of 1: 1.
2. The process for producing a modified polyethylene furandicarboxylate according to claim 1, comprising the steps of:
s10: drying polyethylene furandicarboxylate and polybutylene succinate in a vacuum oven at 80 ℃ for 4 h;
s20: adding the dried polyethylene glycol furandicarboxylate and polybutylene succinate, a chain extender and an antioxidant into a double-screw extruder according to a ratio, and extruding and granulating after melt blending to obtain the modified polyethylene glycol furandicarboxylate granules.
3. The method for preparing modified polyethylene furandicarboxylate according to claim 2, wherein in step S20, the screw rotation speed of the twin-screw extruder is 80-120 rpm; the melt blending temperature is 225-235 ℃, and the melt blending time is 4-8 min.
4. Use of a modified polyethylene furandicarboxylate in a plastic article, characterized in that the modified polyethylene furandicarboxylate is the modified polyethylene furandicarboxylate of claim 1.
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